DSD

Process and plant design of ethanol synthesis from steel industry flue gas
Javier Moreno Fernández-Villamil

PROCESS AND PLANT
DESIGN OF ETHANOL
SYNTHESIS FROM STEEL
INDUSTRY FLUE GAS
Julio 2017
Javier Moreno Fernández-

Villamil
DIRECTORA DEL TRABAJO DE FIN DE GRADO:

Nieves Jimeno Aguilar
1
ACKNOWLEDGEMENTS
I would like to express my gratitude to Professor Tuomas Koiranen from LUT University and
Professor Nieves Jimeno from ETSII University for guiding me with knowledge and patience
through this work. Although the path was not easy, they have helped me overcome many of the
obstacles I found along the way, and thanks to them I can say today I am more confident as a
chemical engineer.
I am also beholden to the friends I made during my stay in Lappeenranta, who have shown me
the true meaning of friendship and intercultural exchange. Special mention to Ali Saud, Anya
Svirelina, Tatiana Orlova, Esther Sanchez and Juancalixto Soto for the many hours spent
together and unconditional support.
Most important of all, I would like to thank my family: my parents, Javier and Paloma, and my
sisters, Paloma and Cristina. Without you, I could have never made it, I feel truly blessed. Thank
you dearly for your everlasting love and care.
I also want to thank Nicholas Marinich for his incessant curiosity and interest in my work. Our
friendship has strengthened more than ever during the past year after your accident- you are a
true inspiration and a model to my life.
Last but not least, thanks to the Lord, my pillar. You have given me everything, and my work is
nothing but an expression of my gratitude to You.
Lima, 15th of July of 2017.
Javier Moreno Fernández-Villamil 1

ABSTRACT
Will we let Europe degenerate into the world’s backyard? No. We are difference makers. In
Lappeenranta University of Technology, we are committed to building an alternative path with
innovative solutions to energy problems that involve recycling as much as possible, leading to a
waste-free world through sustainable and smart business models. The ultimate goal I want to
achieve is to make a difference by proposing an innovative method of ethanol production
through bacterial fermentation from waste gases in the steel industry.
Ethanol obtained through this method falls under the category of second generation biofuels, this
is, fuels made from waste. The growing industry of second generation biofuels is starting to play
a major role in the efforts of the participants of the Paris Agreement to reduce carbon emissions.
As such, it is clear that the motivation behind this work is environmental preservation, but before
discussing technical issues, it must be studied whether there is any potential economic benefit to
this project. This is why the work opens with a brief market review from which it can be
concluded that Finnish and European legislation are to ensure stability and prosperity for those
involved in making commodity fuels and chemicals from waste gases.
Once the economic opportunities of the project are analyzed, a rough draft of the basic design of
the process is presented as a result of an extensive literature review. The goal is to determine the
most efficient and simple solution for the process, which consists of 4 stages: gas pretreatment,
bacterial growth, fermentation and product separation. Feedstock information was supplied by
Outokumpu, whereas process variables and equipment are obtained from the information found
in the articles. On the other hand, the variables that remained unknown are either calculated or
analyzed through sensitivity analysis using Aspen Plus ®.
It is important to understand that the key to the process relies in the fermentation stage. The
small gas to liquid mass transfer rates mean that only a small percentage of the gas is transferred
to the liquid and transformed into ethanol. As a result, gas pretreatment and reactor conditions
must favor high gas to liquid mass transfer rates. This is why the gas is compressed before
entering the reactor, with subsequent cooling to maintain stable temperature in the reactor for
bacteria to be alive. The reactor is also continuously fed with bacteria, which belong to the strain
Clostridium Ljungdahlii, and water, most of which is recycled in the process. After fermentation,
the broth is taken to a distillation column where ethanol is obtained as top product with 84 %
purity in mass. Water, a small quantity of acetic acid, and bacteria are obtained at the bottom,
where a membrane unit separates the bacteria and allows the permeate to be recycled back to the
reactor.
2 Escuela Técnica Superior de Ingenieros Industriales (UPM)

The main obstacles found when making the basic lay out of the process were: designing of a
mathematical model to simulate gas to liquid mass transfer rates, selecting an appropriate reactor
model for this innovative process, defining which pressure the gas should be compressed to
before entering the reactor and defining the capacity of production.
The model developed to simulate mass transfer in the reactor is based on an equation where the
rate of transfer of gaseous substrate into the liquid is driven by the difference in partial pressure
between the gas and the liquid phases. This corresponds with the idea of previously compressing
the gas before fermentation. The reactor model selected is Outotec’s OKTOP 9000 ®, an airlift
reactor currently being investigated by LUT University. Finally, both the pressure of
compression and the capacity of production were fixed by the fact that the bacteria do not allow
a concentration of ethanol above 50 g/L within the bioreactor, otherwise they die. As a result,
sensitivity analysis were performed using Aspen Plus ® in order to determine the total amount of
flue gas to use for the process and its pressure. These values were fixed at 13800 Nm3/h and 3,8
bar, respectively.
Initial process description from the literature review and analysis allowed running simulations
with Aspen Plus ® to further specify process variables and flow conditions, as well as equipment
specifications. All in all, simulation results show an annual productivity of 4888 tons of ethanol.
The simulation stage took the longest time, as several modifications had to be made until the
simulation converged.
Together with the simulated process, a preliminary study of the control of the bioreactor is
presented. A basic piping and instrumentation diagram (P&ID) supports this study. Safety sheets
for the compounds involved in the process and environmental considerations regarding waste
streams are also presented. Along these lines, results show that as much as 1737 tons of carbon
are captured yearly in the process.
Finally, the economic viability of the project is estimated without taking into account any aid
from the EU or the Finnish government for a more conservative approach. According to this
analysis, cash flow of the plant considering a 100 % productivity is 720 000 €. This results in a
payback period of 10 years. Sensitivity analysis for the biggest contributors to costs and benefits
are also included. The use of the waste gases for ethanol productivity is also proved to be more
economically viable than its current use: electricity generation.
Through the use of waste gases as feedstock to make fuel, domestic economic growth is
promoted in a sustainable way by avoiding competition with land, food, and water resources. As
a result, the overall economic, environmental and social impacts of the project are expected to be
beneficial.

TABLE OF CONTENTS
LIST OF TABLES .......................................................................................................................... 6

LIST OF FIGURES ........................................................................................................................ 7
LIST OF SYMBOLS ...................................................................................................................... 8
1. INTRODUCTION ................................................................................................................. 10
2. AIM ....................................................................................................................................... 12
3. METHODOLOGY ................................................................................................................ 13
4. MARKET REVIEW ................................................................................................................. 15
4.1 Biofuel or fossil fuel? .......................................................................................................... 15
4.2 Supply and demand ............................................................................................................. 16
5. PROCESS OVERVIEW AND DESIGN.................................................................................. 19
5.1 Specification of feedstock ................................................................................................... 21
5.2 Gas cleaning and pretreatment ............................................................................................ 21
5.3 Bacterial growth .................................................................................................................. 22
5.4 Gas fermentation ................................................................................................................. 23
5.4.1 Reaction stoichiometry and kinetics ................................................................................ 24
5.4.2 Reactor specifications ...................................................................................................... 25
5.5 Product recovery and separation of bacteria ....................................................................... 31
5.6 Block diagram ..................................................................................................................... 32
5.7 Physical properties of components ...................................................................................... 33
6. DETERMINATION OF PRODUCTION CAPACITY............................................................ 34
7. SIMULATION RESULTS ....................................................................................................... 36
7.1 Process flow diagram .......................................................................................................... 36
7.2 Process description .............................................................................................................. 37
7.3 Simulation diagram ............................................................................................................. 39
7.4 Stream results ...................................................................................................................... 40
7.5 Equipment results ................................................................................................................ 44
8. PROCESS CONTROL ............................................................................................................. 51
9. WASTE TREATMENT AND ENVIRONMENTAL IMPACT .............................................. 54
9.1 Waste management. ............................................................................................................ 55

10. SAFETY ................................................................................................................................. 57

10.1 Safety considerations for carbon monoxide ...................................................................... 57
10.2 Safety considerations for carbon dioxide .......................................................................... 58
10.3 Safety considerations for hydrogen gas............................................................................. 59
10.4 Safety considerations for ethanol ...................................................................................... 61
11. ECONOMIC ANALYSIS ...................................................................................................... 63
11.1 Capital cost estimation ...................................................................................................... 63
11.2 Operation costs .................................................................................................................. 65
11.2.1 Variable costs of operation............................................................................................. 65
11.2.2 Fixed costs of operation ................................................................................................. 67
11.3 Revenue and profitability .................................................................................................. 68
11.4 Sensitivity analysis ............................................................................................................ 71
11.5 Ethanol production vs. electricity generation. ................................................................... 73
12. SOCIAL, ETHICAL AND PROFESSIONAL RESPONSIBILITY. ..................................... 76
12.1 Social issues. ..................................................................................................................... 76
12.2 Ethical and legal considerations. ....................................................................................... 76
12.3 Environmental impact. ...................................................................................................... 76
13. CONCLUSION AND FUTURE PROSPECTIVE. ................................................................ 77
14. SCHEDULING AND BUDGET. ........................................................................................... 80
14.1 Gantt chart. ........................................................................................................................ 81
14.2 Project budget. ................................................................................................................... 82
REFERENCES ............................................................................................................................. 83

LIST OF TABLES
Table 1. Review of main companies currently working on gas fermentation. ............................. 11

Table 2. Exhaust gas composition from different submerged arc furnace processes (SAF) in
Tornio’s steel mill. ........................................................................................................................ 21
Table 3. Main species of bacteria capable of syngas fermentation [31] ....................................... 22
Table 4. Performance parameters of various bioreactor configurations [42] ............................... 26
Table 5. Performance parameters of the OKTOP® 9000 airlift reactor. ...................................... 27
Table 6. Physical properties of the compounds involved in the process [52] ............................... 33
Table 7. Summary of feedstock use, pressures, and ethanol productivity .................................... 35
Table 8. Input and output stream specifications to the overall process. ....................................... 40
Table 9. Global mass and energy balances. .................................................................................. 40
Table 10. Stream results. ............................................................................................................... 41
Table 11. Reactor results summary ............................................................................................... 45
Table 12. Mass, mole, and energy balances for reactor R-101. .................................................... 45
Table 13. Input values and results from DSTWU block. .............................................................. 46
Table 14. . Adjusted input values in RADFRAC column model for T-101. ................................ 46
Table 15. Equipment specifications for T-101.............................................................................. 44
Table 16. Split fraction results for T-101 ...................................................................................... 47
Table 17. Compressor C-101 input values. ................................................................................... 47
Table 18. Compressor C-101 results. ............................................................................................ 47
Table 19. Input specifications for cooler E-101. ........................................................................... 48
Table 20.Cooler E-101 results. ..................................................................................................... 48
Table 21. Input specifications for heat exchanger E-102.............................................................. 49
Table 22. Heat exchanger E-102 results. ...................................................................................... 49
Table 23. Input values for pumps. ................................................................................................ 50
Table 24. Pump results. From left to right, top to bottom: P-101, P-102, P-103, P-104. ............. 50
Table 25. Input, output and consumption of gas in the bioreactor................................................ 54
Table 26. Purchased equipment and total cost after installation of main equipment.................... 64
Table 27. Estimation of total capital investment........................................................................... 64
Table 28. Raw materials consumption and cost............................................................................ 65
Tabla 29. Usage and cost of utilities. ............................................................................................ 66
Table 30. Annual cost for ethanol purification and waste water disposal. ................................... 66
Tabla 31. Fixed operation cost estimation. ................................................................................... 67
Table 32. Cumulative cash flow over life spam and construction of the plant. Technical
shutdown years are highlighted in grey ........................................................................................ 69
Table 33. Representative parameters of the economic interest of the project. ............................. 70
Table 34. Gas inlet and outlet composition and quantities. .......................................................... 73
Table 35. Economic benefit of generating electricity vs. ethanol production. ............................ 75
Table 36. Time distribution for each task. .................................................................................... 80
Table 37. Project budget ............................................................................................................... 82

LIST OF FIGURES
Figure 1.Global fuel ethanol production in 2016. (Country, million gallons; share) [19] ............ 16
Figure 2. EU supply and demand of bioethanol in million liters from 2006 to 2017. [19] .......... 17
Figure 3. Coskata’s integrated biorefinery process to transform biomass into ethanol [24] ........ 19
Figure 4. Possible solution to the transformation of steel mill off gas into ethanol, proposed by
Prof. Tuomas Koiranen as starting course material ...................................................................... 20
Figure 5. Different configurations of bubble-driven bioreactors [42] .......................................... 26
Figure 6. Reactor specifications. ................................................................................................... 28
Figure 7. Specification of kinetics for reactions. .......................................................................... 29
Figure 8. Variation of the mass flow of ethanol obtained at different pressures in the reactor. ... 30
Figure 9. Ternary diagram for water/ethanol/acetic acid system. ................................................. 32
Figure 10.Block diagram for ethanol production through gas fermentation................................. 33
Figure 11. Sensitivity analysis showing ethanol productivity at different quantities of syngas. .. 35
Figure 12. Process flow diagram of ethanol synthesis by gas fermentation. Symbols used comply
with Finnish standards [53] ........................................................................................................... 36
Figure 13. Aspen Plus® simulation diagram. ............................................................................... 39
Figure 14. P&ID for bacterial growth, gas pretreatment and fermentation. ................................. 53
Figure 15. Distribution of cost of manufacturing ......................................................................... 68
Figure 16. Cash flow over the plant’s life spam and construction. ............................................... 68
Figure 17. Net present value at different interest rates, varying from 6 to 14 % .......................... 70
Figure 18. Cumulative cash flow over the years at varying fixed investment costs (± 25 %). ..... 71
Figure 19. Net present value over the plant´s life spam for a discount rate of 10 %. At different
fixed capital investments. Left column represents present scenario. ............................................ 72
Figure 20. Cumulative cash flow over the plant´s life spam at varying ethanol prices (± 10 %). 72
Figure 21. Net present value over the plant´s life spam for a discount rate of 10 % at different
ethanol prices. Left column represents present scenario............................................................... 73
Figure 22. Rankine cycle .............................................................................................................. 74
Figure 23. Gantt chart. .................................................................................................................. 81

LIST OF SYMBOLS
CH3CH2OH Ethanol
CO Carbon monoxide
CO2 Carbon dioxide
H2 Hydrogen
N2 Nitrogen
H2S Hydrogen sulfide
COS Carbonyl sulfide
C10H8 Naphthalene
XBET Ethyl benzene and xylene
US United States
EU European Union
LUT Lappeenranta University of Technology
VTT Technical research center of Finland
IBC Industrial Biotechnology Cluster
P&ID Piping and Instrumentation Diagram
NRTL Non-random Two Liquid Model
HOC Hayden O’Connell
RCSTR Rigorous Continuous Stirred Tank Reactor
KLa Volumetric mass transfer coefficient
H Henry´s constant
PSG Partial pressure of the substrate in the bulk gas
PSL Partial pressure of the substrate in the liquid phase

NSG Moles of substrate transferred from the gas phase into the liquid
VL Volume of the liquid phase
t Time
HVO Hydrogenated Vegetable Oils

MEE Ministry of Employment and Economy

SAF Submerged Arc Furnace
ATCC American Type Culture Collection
BOD Biochemical Oxygen Demand
COD Chemical Oxygen Demand
SCBA Self-contained breathing apparatus
CEPCI Chemical Engineering Plant Cost Index
ISBL Inside Battery Limit Cost
OSBL Outside Battery Limit Cost
R&D Research and Development
NPV Net Present Value

1. INTRODUCTION
As of 2017, most industrial off gases are combusted or even flared. Oil refineries, pulp mills,
power plants and steel mills all over Finland are generating contaminant gases that could be well
transformed into valuable products. Within this context, gas fermentation presents itself as a
novel approach on carbon capture and reuse capable of achieving such a goal [1].
Gas fermentation is based on the capacity of some bacteria strains to thrive off of CO-rich gases
and transform them into commodity chemicals and fuels. These bacteria open the gate to the
continuous production of sustainable biofuels at industrial scale from industrial off gases, an
appealing alternative to the current use of this untapped source of carbon.
Out of all the products obtained in gas fermentation, the one that
receives the most attention is ethanol (CH3CH2OH). This is partly due
to the fact that it is the majoritarian product, but also because of its
value as a renewable fuel. Ethanol is a volatile, flammable, colorless
liquid with a slight characteristic odor. Even if ethanol has less energy
content than conventional gasoline, its high octane value makes it
especially attractive for blending purposes [2].
The value of ethanol as a fuel is well known in Brazil and the United States, where more than 80
million cubic meters of ethanol were produced in 2016 alone [2]. In the US, 97 % of commercial
gasoline contains some ethanol, while in Brazil ethanol’s share accounts for half of the gasoline
market [3,4]. Today, nearly all of the ethanol made in the world is obtained from starch and
sugar-based feedstocks through fermentation with yeasts. This means that the carbon dioxide
released when ethanol is burned is offset with the carbon captured when growing the feedstock
to make it, giving ethanol its renewable fuel label.
Current consumption of oil is 2 liters per person per day, out of which only 0,035 liters come
from the production of renewable fuels from plant biomass [5]. As a result, a 50-fold increase in
the production of renewable fuels is still necessary to completely replace fossil fuels. The use of
plant biomass cannot meet such a demand by itself, due to the limitations on the annual growth
and the energy requirements to break the plant structure; hence the increasing importance of
industrial off gases as potential feedstock for gas fermentation.
Finland is one of the 195 countries that signed the Paris Agreement of the United Nations in
2015, compromising itself to “strengthen the global response to the threat of climate change” and
seeking to keep global average temperature “well below 2 °C above pre-industrial levels” [6].
Reducing the carbon footprint implies reinventing the current use of commodities such as fuels,
and low carbon fuels such as bioethanol are the fastest and most cost-effective way to achieve
this goal [7]. As an example of the current situation in Finland, SSAB’s steel mill in Raahe has
the country’s largest CO2 emissions, with 3,7 million tons produced in a single unit [8].

Given the potential economic and environmental benefits, one may raise questions about the
technical feasibility of gas fermentation as a way of producing ethanol from flue gas. Gas
pretreatment, gas-liquid mass transfer rates, reactor design and bacteria adaptation to the process
are the main challenges for which there is wide ongoing investigation and many questions to
respond. Questions that seem to have been answered already by several (<10) small and middle-
sized companies in the field. Table 1 shows a brief review of these companies. Lanzatech is
probably the most important out of these, with a successful plant in China producing more than
300 tons of ethanol per year from steel mill flue gases. The company is also involved in a project
to build a similar plant in Ghent in cooperation with ArcelorMittal, one of the leaders in the steel
industry.
Table 1. Review of main companies currently working on gas fermentation.

2. AIM
The main objective of this project is to design a process capable of transforming steel mill
industry flue gases into ethanol through gas fermentation.
The project is aimed to contribute to the ongoing investigation by Finnish universities and
institutions such as VTT, LUT University, Aalto University, University of Oulu, and IBC
Finland. In order to specify the problem, it is agreed that the design is made according to a plant
extension of a steel mill in Tornio, which belongs to the company Outokumpu. It is expected that
Outokumpu will provide the information concerning the composition of its exhaust gas as well as
the quantities in which it is produced.
Outokumpu’s steel mill currently employs its exhaust gases for electricity generation. A previous
study of the production capacity of the new plant is needed in order to set a basis for the
simulations and, most importantly, to determine whether ethanol production is more
economically beneficial than electricity generation. A study of the current ethanol market and its
future prospects is also convenient.
The novelty of gas fermentation results in several technical issues that must be addressed despite
the little information available. The most important of these issues is to design a bioreactor that
is capable of delivering enough mass transfer from the gas into the growth media (liquid) to meet
commercial demand. Also, the project design aims to come up with an efficient solution to gas
pretreatment and latter separation of products. With the help of the literature, a proposal for the
process will be made, and later assessed through simulations in Aspen Plus ®. To simplify the
process, it is agreed that the final product is ethanol with 84 % purity in mass. The targeted
purity of 96 % will be achieved through the use of an external service (e.g. Finnish company St1).
Furthermore, it is decided that the ethanol obtained in the process is to be used for fuel transport
purposes.
Finally, the project will conclude with an economic evaluation of the proposal and an assessment
of the impact, which will entail mainly environmental benefits and disadvantages.
These objectives are to be met as part of an introductory course on plant design, hence the
superficial depth at which the concepts are covered. Given the available time and resources, it is
important to clearly define the scope of the project at each point, leaving out any secondary
details which in a real project would have to be specified.

3. METHODOLOGY
This project is made according to the standard guidelines established by Professor Tuomas
Koiranen on the Process and Plant design course from Lappeenranta University of Technology
(LUT):
 First, a market review is necessary to determine the current situation of the product
(ethanol) in the Finnish economy and its future prospect. Prices, taxation, distribution
networks and main players in the renewable fuels market are discussed to ensure the
economic viability of the project.
 Next, process options and technology are presented through a literature review of the
process. The different alternatives are assessed and a final preliminary design is presented:
block and flow diagrams, process conditions, and preliminary specifications of the
equipment, as well as feedstock specifications.
 The off gas is currently used to generate electricity. The advantages of using the flue gas
to produce ethanol instead of generating electricity with it are studied. To do so, the
production capacity is calculated, and the potential benefits are compared to the current
savings in electric power.
 The selected process is simulated through Aspen Plus®. Several simulation runs are
made until the desired process conditions are achieved and the solution converges. Flow
composition and conditions, as well as detailed equipment specifications are obtained.
Results are evaluated and presented. Heat integration of the plant is considered to be out
of the scope of the course.
 A preliminary study of the control of the bioreactor is presented. A basic piping and
instrumentation diagram (P&ID) supports this study. Safety sheets and environmental
considerations regarding the process, the products and the raw materials are also
presented.
 Once the equipment and the flows are properly defined, investment and operational costs
and profitability are estimated to evaluate the economic feasibility of the venture.
Reliability of the results is assessed with a sensitivity analysis. In addition, an evaluation
of the environmental impact of the new plant is presented. Waste water treatment, raw
material and product hazards, and reduction in carbon emissions are the main points
considered.
 Finally, the project concludes with recommendations for future studies, as well as an
estimation of the work hours and schedule organization (Gantt chart).

Given the presence of acetic acid in the process, it is decided that the NRTL thermodynamic
model with the Hayden O’Connell (HOC) correction is the most suitable one for the simulations
in Aspen Plus® in order to calculate liquid-vapor equilibrium [9]. The procedure and initial
assumptions for the simulation of the reactor and the distillation column are briefly introduced
below:
Reactor simulation
The reactor selected for the simulation is RCSTR (Rigurous Continuous Stirred Tank Reactor).
Through its rate selection option, this option allows modelling the bottleneck of the process:
mass transfer from the bulk gas into the liquid. This means that the pace of the reaction is
determined by the rate of transfer from the gas to the liquid, which can be expressed through the
following equation [10]:
𝑺
𝑺 𝑺 = 𝑺 𝑺 ∙ (𝑺𝑺 − 𝑺 𝑺) (1)
𝑺 𝑺
𝑺𝑺𝑺𝑺 𝑺
𝑺
According to Equation 1, the driving force of this process is the
difference in partial pressure between the bulk gas and the liquid.
The rate of transfer is also linearly dependent in the K La value of
the reactor (inherent to the type of bioreactor used and the
hydrodynamic regime) and the Henry’s law constant, which
refers to the solubility of the gas into the liquid. In addition and
for simplicity reasons, it is assumed that the partial pressure of
the gas in the liquid tends to zero (𝑺𝑺𝑺 = 𝑺), as it is assumed that
the molecules react immediately in the liquid medium.
Distillation simulation
The simulation of the distillation column is done according to the lecture notes from the
“Operaciones de Separación I” course taught by Santos Galán in ETSII University. The
procedure is the following:
1. Predesign calculations through the Fenske equations to estimate distillate and bottom
products and compositions. The rules of thumb proposed by Seader and Henley [11] are
used to determine pressure in the column and type of condenser (total, partial…).
2. Simulation with the DSTWU block. This rough model uses the previous results as an
input to provide approximate values for the reflux ratio, number of stages, feed stage,
duties and distillate to feed fraction.
3. Rigorous simulation and optimization using RADFRAC option and the results from the
previous step as input values. If the results do not meet the requirements, the Design of
specifications module shall be used to optimize them.

4. MARKET REVIEW
The market review aims to provide a clear image of the current situation of the ethanol market,
more specifically in the European continent. The main objective is to expose the potential
economic benefits of this venture, a crucial step of any engineering project. In order to justify
proceeding with the next stages, the market review needs to clearly define the product (what will
be sold?), its supply and demand, its commercialization, as well as an educated guess on the
future state of the ethanol market.
4.1 Biofuel or fossil fuel?
Ethanol markets are varied: from recreational use in alcoholic beverages to solvent for paints or
industrial precursor for organic compounds such as diethyl ether or acetic acid. Nonetheless, it is
without a doubt that the use of ethanol as a transport fuel is the most important market of all,
with the highest beneficial impact on the environment. From 2000 to 2007, world ethanol
production for transport fuel tripled from 17 billion to more than 52 billion liters [12]. It is
because of this reason that herein the project aims to the production of ethanol for transport
purposes.
The department of Energy of the European Commission defines biofuels as “liquid or gaseous
transport fuels such as biodiesel and bioethanol which are made from biomass.” [13]. According
to this definition, ethanol produced from industrial off gases is not bioethanol. Furthermore, it is
important to note that the mill industry off
gas is fossil-derived, and thus so is the
ethanol obtained from it. This label has a
negative impact on the product, not only
because it worsens its marketing image, but
also because it does not allow it to benefit
from the tax exemptions that the European
Union is offering to boost the biofuel
industry.
However, is it fair to give ethanol produced from industrial waste gases such a label? Companies
such as Lanzatech, a pioneer in the carbon recycling industry, does not believe so. Obtaining
ethanol from waste industrial gas is beneficial to the environment, as it implies reusing otherwise
contaminant gases to produce commodities whilst simultaneously reducing the carbon footprint.
And the European Union agrees. This is why it has granted a 10.2 million € subsidy to help build
Lanzatech’s biorefinery in Ghent, which will transform steel mill off gas into ethanol [14]. The
subsidy is part of the Horizon 2020 program, which aims to “securing Europe's global
competitiveness” by “coupling research and innovation” [15].

It is expected that the lobbying made in this field will result in a change of definition, as already
some institutions such as the Business Dictionary are including industrial off gases as feedstock
in their definition for biofuels [16].
Regarding regulations and definition of the product, ethanol produced from mill industry flue
gases is from here on to be considered bioethanol, given the situation. As such, tax exemptions
and subsidies are taken into consideration for this review as well as the economic analysis.
Another benefit is the improved image of the product, which helps its commercialization. Also,
market data available for bioethanol from biomass is to be used in the study, with due
reservations.
4.2 Supply and demand
It is clear that the motor that propels the biofuel industry is not only economical, but also
environmental. Transforming waste into commodities such as valuable chemicals and fuels has
the power of increasing the revenue of facilities such as steel mills, while reducing the carbon
footprint. As a result, companies around the world are starting to think of waste gases as an
opportunity of investment, rather than a liability. The European Union, in an attempt to meet the
requirements of the Paris Agreement of 2015, is targeting to increment the use of renewable
energy in transport to 10% by 2020. Finland is one step forward, targeting a 20% share of
biofuels used in transportation by 2020, and 30 % in the year 2030 [17]. This includes biofuels
made from vegetable oils, fat, cellulose, and industrial waste.
As seen from Figure 1, the United States and Brazil dominate ethanol production worldwide
producing 58 and 28 billion liters in 2016, respectively. With 5 billion liters, the next biggest
producer is the European Union (5 % global share), where the largest producers are France,
Germany and Hungary [16]. In Finland, ethanol production is reduced and mainly based on
collected household, commercial and industrial bio-waste and residues. Also, ethanol is produced
from the food and baking industry using decentralized production methods from side-streams
[18].
Figure 1.Global fuel ethanol production in 2016. (Country, million gallons; share) [19].

In the year 2014, ethanol production in the European Union reached its peak at 5,3 billion liters,
as seen in Figure 2. The situation was favorable due to low feedstock values and restrictive
measures on imports, resulting in an increase in production. At the same time, consumption fell,
making Europe self-sufficient on bioethanol. This situation was prolonged in 2015, with a slight
decrease in production to around 5,2 billion liters, which is equivalent to 32,6 million barrels of
crude oil [19].
Figure 2. EU supply and demand of bioethanol in million liters from 2006 to 2017. [19].
It is expected that the production of ethanol in the EU will again slightly decrease to around 5,1
billion liters in the year 2017. The market is suffering mainly due to a reduction in gasoline
consumption and new regulations imposing a 7 percent cap on food based biofuels. This
reduction in demand, which has been going since 2011, is responsible for the consequent decline
in supply. Theoretical crush margins have been positive since the year 2015, but the bioethanol
industry in many European countries is suffering from financial problems: lack of capital and
profitability, competition from imports, limited availability of crops for feedstock and decline in
gasoline prices are the main issues [20].
The dim situation in which the European bioethanol market finds itself has opened the gateway
for second generation biofuels, these are, biofuels which are generated from waste: hydrogenated
vegetable oils (HVO), cellulosic ethanol, and ethanol generated from industrial waste gases. In
addition, the European Union is making sure only the most efficient plants keep functioning,
complying with its objective to reduce greenhouse gas emissions in the following years. The
substantial incentives offered by the EU as part, for instance, of the Horizon 2020 program are
responsible for the current success of the second generation biofuel industry.

Furthermore, the biofuel market in Finland is ensured to prosper due to a national law that
requires fuel distributors to provide biofuels to the market [21]. A recent study on the 2030 EU
climate targets concluded that the most cost-effective way to reduce emissions in Finland is to
invest in the production and consumption of domestic second generation biofuels, including
those obtained from industrial waste gases. This situation leads to a growing ethanol domestic
market in the country, as seen from the increasing production of ethanol by the company St1
Biofuels [22], all with governmental support. An example of this funding is the 30 million €
received by Suomen Bioetanoli Oy from the Ministry of Employment and Economy (MEE) to
build its straw based ethanol plant in Myllykoski [23]. Other big companies in the Nordic fuel
market such as Neste Corporation in collaboration with Boeing are promoting the
commercialization of renewable aviation fuel.

5. PROCESS OVERVIEW AND DESIGN
The transformation of steel mill off gases into ethanol is a novel process for which there is little
disclosed information. Nonetheless, gas fermentation to obtain ethanol and other commodities
from biomass is a mature technique widely used in Brazil and the United States. The only
difference to take into consideration is that the transformation of biomass to ethanol requires a
previous additional step to convert the feedstock into syngas, a process known as gasification.
Figure 3 shows a conceptual view of the transformation of this process, according to Coskata’s
integrated biorefineries:
Figure 3. Coskata’s integrated biorefinery process to transform biomass into ethanol [24].
When using exhaust gases from a steel mill, the gasifier becomes unnecessary. The result is a
plant with four main operations: gas cleanup and pretreatment, bacterial growth, fermentation,
and product separation. One possible solution for the process is proposed in Figure 4 as part of
the starting course material by Professor Tuomas Koiranen. However, this is only one proposal,
and appropriate changes shall me made according to the literature review in the following
paragraphs. The aim is to determine key equipment specifications and processing conditions that
result in an efficient and robust process, feasible at industrial scale. This final solution is to be
supported by the results from the simulations and the economic assessment.

Figure 4.Possible solution to the transformation of steel mill off gas into ethanol, proposed by Prof. Tuomas Koiranen as starting course material.

5.1 Specification of feedstock
Exhaust gases are obtained at different points in the steel making process (furnaces and ovens).
These gases contain a mixture of carbon monoxide (CO), hydrogen gas (H2), and carbon dioxide
(CO2) in different compositions, also known as syngas. In addition, the exhaust gases contain
nitrogen gas (N2) and dust particles, as well as other impurities in trace quantities (<1%) [25]. In
Outokumpu’s Tornio steel mill, the exhaust gases stem from the submerged arc furnace process
during ferrochromium production. The specifications in quantity and composition are shown in
the following table:
Table 2. Exhaust gas composition from different submerged arc furnace processes (SAF) in Tornio’s steel mill.
Average
Volume
Furnace CO % H2 % CO2 % N2 % Volume CO % H2 % CO2 % N2 %
(Nm3/h)
(Nm3/h)
SAF1 8000 88 3,6 1,7 6,7 8000
SAF2 14000-16000 87 4,8 5,2 3 15000
SAF3 22000-24000 84 3,9 6 6,1 23000
SUM 46000 86 4 5 5
Outokumpu also provided information regarding the temperature and dust particles of the gas.
According to this information, the gases exit the furnaces at 800 °C and contain, in average, 60
mg/m3 of fine dust particles of around 10 µm in diameter. However, Outokumpu uses cooling
units and bag filters in its plant as part of its particle recycling operation. After cleaning, gas
temperature is 30 °C, pressure is atmospheric, and particle density is at 5 µg/m3 [26]. Impurities
are not specified as they are present in trace quantities and they are harmless to the bacteria, as
explained by many authors [27, 28]. Gas pretreatment and conditioning is further discussed in
the following paragraphs.
5.2 Gas cleaning and pretreatment
Before the off gases coming from the furnaces can be transformed into ethanol, some previous
20 Escuela are
conditioning is necessary. Two main operations Técnica Superior
carried out indethis
Ingenieros
processIndustriales (UPM)
in the following
order:
 Gas cleaning: reduction of dust particle density to avoid mechanical problems in the
upstream equipment. As mentioned earlier, this step is already carried out by Outokumpu.
 Gas pretreatment: achieving necessary temperature and pressure for the fermentation
process to take place efficiently. Pressure is raised with a compressor in order to improve
gas-liquid mass transfer rates, while temperature is lowered using a heat exchanger to the
optimal value for bacteria to perform. The optimal pressure for the gas stream to enter the
bioreactor will be studied using the sensitivity analysis tool from Aspen Plus®. On the
other hand, temperature is settled by bacteria specifications, which will be discussed in

the following section.
As mentioned earlier, the possible presence of trace gases is not taken into consideration.
Common contaminants found in steel mill gases include: sulphur compounds (H2S, COS),
benzene, toluene, ethyl benzene and xylene (XBET), and naphthalene (C10H8) [29]. In addition,
oxygen gas can be present due to leaks in the transportation or in the pretreatment operations, but
it is removed by oxidation of dead cell material [30]. On the other hand, gaseous sulphur
compounds are beneficial to the bacteria, while the rest of these contaminants do not pose a
threat to the bacterial activity at trace quantities [25]. Nitrogen gas is also innocuous. Its presence,
however, reduces efficiency by lowering the partial pressure of other gases. Nonetheless, given
its low presence in the gas, it is decided that the cost of removing it is greater than the losses in
efficiency derived from its presence.
5.3 Bacterial growth
Table 3 contains the main bacteria species capable of transforming carbon monoxide and
hydrogen into valuable products such as ethanol, acetate, and 2, 3-butenediol. These bacteria can
be divided into two groups: mesophilic and thermophilic. As such, while mesophilic
microorganisms have optimal growth temperatures between 37 and 40 °C, optimal temperatures
for thermophilic bacteria vary between 55 and 80 °C. Favorable pH values, on the other hand,
vary between 5,8 and 7 depending on the species.
Table 3. Main species of bacteria capable of syngas fermentation [31].

Out of all the species mentioned in Table 3, the one that has been most widely studied is
Clostridium Ljungdahlii. It was the first microorganisms discovered to be capable of
transforming CO and H2 rich gases into ethanol and acetic acid. C. Ljungdahlii is a rod shape,
gram positive anaerobic bacteria, with optimal reported growth temperature and pH values of
37 °C and 6, respectively [32]. Given the sensitivity of bacteria to these conditions, it is essential
to ensure these values are kept constant in the bioreactor and the growth media with proper gas
pretreatment and control of the operations.
C. Ljungdahlii will be used for the design of the project, due to the extensive research available
and the unclear differences in performance between strains. Before implementation, the bacteria
needs to be adapted to the process to ensure its efficiency. Genetic engineering tools are used to
make necessary changes in the genome, but details of this process are left out of the scope of this
project.
Before being fed to the bioreactor, the bacteria are grown in a stirred tank. The tank is fed with
water and nutrients containing mainly glucose. The components which need to be supplied for
growth are standardized according to the type of bacteria and the desired end products. For C.
Ljungdahlii, American Type Culture Colletion (ATCC) medium 1754 is used [31]. Residence
time in the medium is adjusted to the time needed to grow C. Ljungdahlii: 36 hours [33]. It is
assumed that the bacteria that are fed to the growth medium weight only 10 % of their final
weight after growth, and that no nutrients leave the tank.
After growth, the bacteria are pumped into the bioreactor at a concentration of 155 g/L. Cell
concentration within the reactor is fixed at 20 g/L, while residence time is adjusted according to
the life spam of bacteria: 77 hours [34]. The rate at which ethanol is removed must be carefully
monitored as to not exceed a 5 % concentration (50 g/L) in the bioreactor, above which ethanol
becomes toxic for the bacteria [35]. Temperature and pH values are also important, as mentioned
earlier. For both the bioreactor and the stirred tank, temperature and pH values are kept at 37 °C
and 6, respectively.
Other specifications regarding biological activity of the bacteria and synthesis paths from syngas
to ethanol or acetic acid are considered irrelevant and are therefore left out of the scope of the
project.
5.4 Gas fermentation
Fermentation is the most important step of the process. It takes place in a bioreactor, where the
liquid medium containing the bacteria is put into contact with the compressed syngas. The
effectiveness of the contact between phases is what determines the profitability of the project and
its scale up to meet industrial demand. This is due to the low solubility of CO and H2 (28 and 1,6
mg/L at 1 atm and 293 K [36]), which results in high mass transfer resistance between the liquid
and the gas phase. As a result, it is of paramount importance to pay special attention to bioreactor
design and gas pretreatment parameters, in order to achieve efficient mass transfer rates that

yield a profitable process at industrial scale. These parameters include: turbulence, bubble break-
up, CO and H2 partial pressures and gas residence time [37]. The reader could think that
temperature should also be considered, but the need to keep the bacteria alive already fixes this
value and therefore it cannot be changed.
5.4.1 Reaction stoichiometry and kinetics
After dissolving into the liquid, gaseous substrates undergo the Woody-Ljungdahlii pathway, a
chain of biochemical reactions catalyzed by the bacteria. The outcome can be summarized in the
following chemical reactions [38]:
6 𝑺𝑺 + 3 𝑺2𝑺 ⟶𝑺2𝑺5𝑺𝑺 + 4 𝑺𝑺2 ∆𝑺 = −217,9 𝑺𝑺/𝑺𝑺𝑺 (2)

2 𝑺𝑺2 + 6 𝑺2 ⟶𝑺2𝑺5𝑺𝑺 + 3 𝑺2𝑺 ∆𝑺 = −97,3 𝑺𝑺/𝑺𝑺𝑺 (3)
4 𝑺𝑺 + 2 𝑺2𝑺 ⟶𝑺𝑺3𝑺𝑺𝑺𝑺 + 2 𝑺𝑺2 ∆𝑺 = −154,9 𝑺𝑺/𝑺𝑺𝑺 (4)
2 𝑺𝑺2 + 4 𝑺2 ⟶𝑺𝑺3𝑺𝑺𝑺𝑺 + 2 𝑺2𝑺 ∆𝑺 = −75,3 𝑺𝑺/𝑺𝑺𝑺 (5)
As seen from reactions 2 to 5, bacteria catalyze the reactions between water and the gaseous
compounds present in the syngas to yield ethanol and acetic acid. There is wide ongoing
investigation regarding the selectivities of the reactions. Researchers at VTT, in collaboration
with LUT University, have reported to this team ethanol to acetic acid ratios of 10:1. Therefore,
it is assumed that selectivity for competitive reactions 2 and 4 and 3 and 5 respectively is 10.
As mentioned, the rate-limiting step in reactions 2 to 5 is the dissolution of the gaseous

substrates CO and H2 into the liquid, which can be modeled by the following kinetic equation
[39]:
𝑺
𝑺 𝑺 = 𝑺 𝑺 ∙ (𝑺𝑺 − 𝑺𝑺) (6)
𝑺 𝑺
𝑺𝑺𝑺𝑺 𝑺
𝑺
Where 𝑺𝑺𝑺 is moles of substrate transferred from the gas phase into the liquid, 𝑺𝑺 is the volume
of the liquid phase, t is time, 𝑺𝑺 is the overall mass transfer coefficient, a is the gas-liquid
interfacial area per unit volume, H is Henry’s law constant, 𝑺𝑺𝑺 is the partial pressure of
𝑺
𝑺 𝑺 and in the partial pressure of the substrate in the liquid
the substrate in the bulk gas,
phase.

It is assumed that the gaseous substances react instantly when dissolved in the liquid, which
makes their partial pressures in the liquid phase 𝑺𝑺𝑺 tend to zero:
𝑺𝑺𝑺 = 𝑺 𝑺 ∙ 𝑺 ∙ 𝑺 (7)
𝑺
𝑺𝑺𝑺𝑺 𝑺 𝑺
𝑺
Since their solubilities are the smallest in each reaction, the limiting compounds are hydrogen
and carbon monoxide. As a result, the kinetic equations are referenced to each of these
compounds. The Henry constant values at 37 ⁰C for CO and H2 are [40]:
𝑺𝑺
𝑺37⁰𝑺 = 8,11 ∙ 10−6 ( )
𝑺𝑺
𝑺3𝑺𝑺
𝑺𝑺
𝑺37⁰𝑺 = 7,3 ∙ 10−6 ( )
𝑺2 𝑺3𝑺𝑺
The overall mass transfer coefficient (𝑺𝑺) and the gas-liquid interfacial area per unit volume (a)
are grouped in a single term known as the volumetric mass transfer coefficient or Kla (h-1). This
value is widely used to describe the efficiency of gas to liquid mass transfer rates in bioreactors,
and is heavily dependent on its design and the hydrodynamic conditions within. In the following
paragraphs, reactor design and parameters are discussed.
5.4.2 Reactor specifications
Continuous stirred reactors (CSTR) have been traditionally used for gas fermentation processes
[41]. Advantages of stirred reactors include excellent mixing and homogeneous distribution of
the gaseous compounds to the microorganisms. However, they have been used mostly at
laboratory scale. Their application at industrial scale for gas fermentation is challenging, due to
the high power per unit volume required, which renders the operation economically unprofitable
[42]. Therefore other, less energy-demanding reactor configurations have been widely studied in
the past years for syngas fermentation. The main ones include bubble column, trickle bed,
monolithic, and airlift reactors. Table 4 contains a brief overview of the performance parameters
for different bioreactor configurations, according to the literature [43, 44, 45].

Table 4. Performance parameters of various bioreactor configurations [42].
According to Table 4, KLa values are the greatest in packed columns with co-current flow,
followed by bubble columns equipped with microbubble spargers. For each reactor type, K La
values vary considerably, as they are based on peer reviews with many different experimental
conditions. This variation makes it difficult to establish a clear comparison between reactor types.
Given the situation, the decision is guided by the maturity of the technology, as well as the
amount of information available on it. In that case, the reactor that seems most suitable for this
process is a bubble column reactor.
Bubble column reactors are designed for industrial applications with large working volumes.
They are remarkable for their mechanical simplicity and low power consumption: energy to
enhance mass transfer is not supplied by moving parts, but through sparged air. As a result, their
main advantages are low operational and maintenance costs and high mass and heat transfer rates,
while coalescence and back mixing are their main drawbacks [46]. Internal structures that
modify the flow characteristics and make up for these disadvantages have aroused interest in the
past years [47]. One such modification is the airlift reactor, where riser and downcomer channels
distribute the gas all along the geometry of the reactor, improving the hydrodynamics [48].
Figure 5. Different configurations of bubble-driven bioreactors [42].

Professor Tuomas Koiranen, coordinator of the project, has expressed his interest in the use of an
airlift reactor designed by Finnish company Outotec®. The reactor is now under study by
different projects in LUT and Oulu universities, and Outotec has provided all the necessary
information about it. The commercial name for the reactor is OKTOP® 9000, and it consists of
an airlift reactor specially designed for each purpose. The team considers that even if bubble
column reactors are the most conservative approach for the design of this project, the use of the
OKTOP® 9000 has the following advantages:
 Extensive information provided by the company.
 Guaranteed satisfaction of technical demands such as mass and heat transfer rates.
 Reliable support and guidance by a local company, boosting national economy and
eliminating dependence on international services or companies.
On top of these, Prof. Tuomas Koiranen’s interest is taken into account and the team accepts to
use the OKTOP® 9000 airlift reactor for the design of the project. The performance parameters
from the OKTOP® 9000 are shown in Table 5:
Table 5. Performance parameters of the OKTOP® 9000 airlift reactor.
Volume 900 m3
Height 20 m
K La 18 h-1
Gas Retention Time 10-20 hr
Liquid Retention Time 2-2.5 min
Gas Holdup 20-30%
The reactor model used for simulation in Aspen Plus® is RCSTR, as already mentioned.
Temperature is fixed by the bacteria at 37 °C, while pressure in the top of the reactor is
atmospheric. The RCSTR block allows to model the kinetics of the reactions that take place
according to Equation 7. The driving force is the partial pressure of the gas with least solubility
(CO or H2), while the kinetic constant is the product of the KLa and the Henry constant of the gas
at 37 °C. The selectivity of competitive reactions is implicit in the fact that the kinetic constant is
ten times bigger in those reactions that yield ethanol as a product:
6 𝑺𝑺 + 3 𝑺 𝑺 ⟶𝑺 𝑺 𝑺𝑺 + 4 𝑺𝑺 𝑺 = 4,01 ∙ 10−8 ( ) (8)

𝑺
𝑺𝑺
2 2 5 2
𝑺3𝑺𝑺 ∙

2 𝑺𝑺 + 6 𝑺 ⟶ 𝑺 𝑺 𝑺𝑺 + 3 𝑺 𝑺 𝑺 = 3,65 ∙ 10−7 ( ) (9)
𝑺𝑺𝑺
2 2 2 5 2
𝑺3𝑺𝑺 ∙
𝑺
4 𝑺𝑺 + 2 𝑺 𝑺 ⟶𝑺𝑺 𝑺𝑺𝑺𝑺 + 2𝑺𝑺 𝑺 = 4,01 ∙ 10−9 ( ) (10)
𝑺
𝑺𝑺
2 3 2
𝑺3𝑺𝑺 ∙
𝑺
2𝑺𝑺 + 4 𝑺 ⟶ 𝑺𝑺 𝑺𝑺𝑺𝑺 + 2 𝑺 𝑺 𝑺 = 3,65 ∙ 10−8 ( ) (11)
𝑺𝑺𝑺
2 2 3 2
𝑺3𝑺𝑺 ∙
𝑺
Figures 6 and 7 show the input values for temperature, pressure, volume and kinetics of reactions
introduced in the RCSTR block in Aspen Plus®. Reactor pressure is chosen as the mean between
the pressure of the compressed syngas and the pressure at the top of the column (atmospheric
pressure), since the RCSTR model does not allow to simulate the pressure variation that the gas
experiences as it rises.
Figure 6. Reactor specifications.
The need for the syngas to overcome the hydrostatic pressure in the bioreactor imposes a
minimum value for its incoming pressure. The hydrostatic pressure at the bottom P depends on
the reactor height H, density of liquid medium 𝑺 (considered as that of the water), and the gravity
constant g:

𝑺𝑺
𝑺 = 𝑺 ∙ 𝑺 ∙ 𝑺 = 1000 ⁄ ∙ 9,8 𝑺⁄𝑺 2 ∙ 20 𝑺 = 294000 𝑺𝑺 = 1,96 𝑺𝑺𝑺 (12)
𝑺3

Figure 7. Specification of kinetics for reactions.
Pressure in the reactor is fixed at 1,5 bars, according to Figure 6. This value is, as explained, the
mean between the minimum pressure for the incoming gas (≈2 bars) and the atmospheric
pressure. According to equation 7, however, increasing the partial pressure of CO and H2 will
increase conversion of syngas into ethanol. Therefore, the effect on syngas conversion to ethanol
from increasing the pressure of the syngas is studied. In order to reach an agreement between
profit from increasing ethanol titers and the cost of compression, the sensitivity analysis block
from Aspen Plus® is a useful tool. The amount of ethanol obtained at different pressures of the
compressed syngas is shown in Figure 8.

Figure 8. Variation of the mass flow of ethanol obtained at different pressures in the reactor.
The sensitivity analysis results prove, as expected, that ethanol titers increase by increasing the
pressure of the incoming gas. Given the slope of the graph in Figure 8, the increase in the cost
from electricity from compression is likely to be less than the increase in benefit. However,
bacteria within the reactor do not survive in concentrations of ethanol bigger than 50 g/L. With a
residence time of 77 hours and a volume of 900 m3, the fermentation broth containing bacteria
and the products must be removed at a rate of 11,7 m3/hr. At a concentration of 50 g/L, this is
584,4 kg/hr of ethanol. As a result, while the hydrostatic pressure sets a lower limit for incoming
gas pressure, the maximum concentration allowed by the bacteria fixes its upper limit. Final
pressure in the reactor will be fixed once the exact amount of feedstock to use in the process is
determined, according to the desired capacity of production.
Finally, there is one more free variable regarding the simulation of the bioreactor: amount of
bacteria in the feed. The amount of bacteria in the feed will be dependent on their life spam
inside the reactor (77 hours), as well as the reactor volume (900 m3) and cell concentration (20
kg/m3). The calculation is as follows:
𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺 𝑺ℎ𝑺

∙ 900 𝑺3 = 18000 𝑺𝑺 (13)
𝑺𝑺⁄ 𝑺3
𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺: 20
18000 𝑺𝑺 𝑺𝑺⁄
𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺 𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺: = 233,8 (14)
77 ℎ𝑺𝑺𝑺𝑺 ℎ𝑺
Since bacteria are fed to the reactor at a concentration of 155 g/L, volumetric flow of water in
this stream is fixed at 1,5 m3/hr.
5.5 Product recovery and separation of bacteria
Distillation has been commonly used to separate mixtures containing ethanol, water, and other
fermentation products [49]. The main drawback from this technology is that it is an energy
intensive operation, and therefore potentially expensive. Nevertheless, the cost of product
separation is expected to be smaller than the cost of fermentation, so other, less studied
technologies such as gas stripping, liquid-liquid extraction, pervaporation and vacuum
distillation are neglected. Furthermore, the energy generated in the fermentation process (note all
reactions are exothermic) could be potentially used in the distillation column as part of a heat-
integrated process, reducing the cost of the operation.
Thermodynamic properties at 1 bar regarding the separation of a mixture containing water,

ethanol and acetic acid are illustrated in the ternary diagram in Figure 9. In it, the presence of the
water/ethanol azeotrope is clearly noticeable, which is the main responsible for the amount of
energy needed in this operation. The azeotrope has a boiling point of 78,1 °C and a mass
composition of ethanol of 95,6 % [50]. The azeotrope is obtained as distillate, given its higher
volatility, while a mixture of water and acetic acid, containing also the bacteria, is obtained as
bottom product.
As specified earlier, further purification of ethanol is neglected for simplicity reasons. An

external service such as ST1 is to be considered for this operation. Furthermore, the recovery of
acetic acid to increase benefit is also neglected due to the small amounts in which it is expected
to be obtained.
The bottom products containing mainly water, acetic acid and bacteria are recycled back to the
reactor after removing the bacteria and purging. For the removal of bacteria, standard,
microfiltration membranes are used.

Figure 9. Ternary diagram for water/ethanol/acetic acid system.
Lanzatech has recently studied the possibility to increase profitability of gas fermentation by
increasing product portfolio. Indeed, it is possible to obtain valuable products such as 2,3-
butenediol from genetically modified Clostridium Ljungdahlii [51]. However, this field is still
under wide research, and its industrial implementation will have to wait a few more years before
taking place.
5.6 Block diagram
Figure 10 illustrates the proposed block diagram of the process. The diagram has been
constructed according to the literature review and the objective of designing an efficient and
robust gas fermentation process, feasible at industrial scale. Whether this objective is met or not
will be verified according to simulation results and the economic analysis.
.

Figure 10.Block diagram for ethanol production through gas fermentation.
5.7 Physical properties of components
Physical properties regarding the compounds involved in the process are illustrated in the
following table:
Table 6. Physical properties of the compounds involved in the process [52].
Boiling Density
MW Water solubility
Compound Formula point (g/mL at pKa (at 25 ºC)
(g/mol)¹ (g/100 mL at 25ºC)
(ºC) 20ºC)
Water H₂O 18,02 100 - 0,9982 14
Carbon
CO 28,01 -192 0,0028 1,166 E -03 -
monoxide
Carbon
CO₂ 44,01 -78,5 0,1688 1,842 E -03 -
dioxide
Hydrogen H₂ 2,02 -252,7 0,00016 8,429 E -05 -
Ethanol C₂H₆O 46,07 78,4 Miscible 0,79 15,9
Acetic Acid C₂H₄O₂ 60,05 118,1 Miscible 1,05 4,76

6. DETERMINATION OF PRODUCTION CAPACITY
Estimating the capacity of production is a necessary step in order to:
 Fix the amount of feedstock needed for the process.
 Determine the amount of ethanol that can be obtained from that amount of feedstock.
 Determine if the production of ethanol from flue gas is more profitable than using it to
generate electricity.
As discussed, ethanol production is dependent on the partial pressure of the incoming gases CO
and H2 and the configuration of the bioreactor (including hydrodynamic conditions). With the
latter fixed, the free variable that determines the productivity of ethanol is the pressure at which
the gas is compressed. This pressure must be high enough so that the gas can overcome the
hydrostatic pressure at the bottom of the reactor (2 bars). The upper limit to the productivity is
imposed by the concentration of ethanol at which the bacteria can survive: 50 g/L. This gives, as
already discussed, 584,4 kg/hr of ethanol.
One may ask whether adding more reactors to the process could be an option to increase
productivity. The reactors could be disposed in parallel or in series, and as a result productivity
could be increased. However, since the project is part of a pilot plan still under exhaustive study,
it is decided that one reactor is the best option for now, disregarding economy of scale.
The question that arouses is the impact that syngas flow has on productivity. 45000 Nm3/hr of
syngas is an excessive amount of gas for a 900 m3 reactor, and technical problems due to
excessive gas velocity and bubble coalescence can be expected. Furthermore, low conversions
imply that a lot of gas will not be consumed in the process, which is translated into wasted
electricity from its compression.
According to the ideal gas model, if total pressure and molar fractions within the gas are kept
constant, then the partial pressure remains the same and productivity does not vary. However, the
model is not ideal, so small changes can be expected in productivity by varying the total pressure.
On the other hand, limiting compounds such as hydrogen (4 % in composition) will make
productivity drop at a certain point if not enough feedstock is supplied to the process. The
expected results are confirmed by the sensitivity analysis illustrated in Figure 11, where the
effect of feedstock amount on ethanol productivity is studied. Small changes in productivity take
place by varying the use of the total feedstock from 25 to 100 %. This is a result of the non-ideal
behavior of the gas, as explained. Under 25 %, productivity drops, most probably due to the
depletion of all the hydrogen.

Figure 11. Sensitivity analysis showing ethanol productivity at different quantities of syngas.
The idea is to use only 30 % of syngas coming from the steel mill (conservative approach based
on sensitivity analysis results) and readjust the pressure at which it is compressed to a value that
yields the desired amount of ethanol (584 kg/hr). The sensitivity analysis tool is once again used
to determine these values, which are shown in Table 7.
Table 7. Summary of feedstock use, pressures, and ethanol productivity.
Adjusted variables based on productivity and feedstock use

Volumetric flow of syngas 13800 Nm3/hr (30 %)
Pressure of compressed gas 3,8 bar
Pressure in the reactor 2,4 bar
Ethanol production 587,5 kg/hr
With feedstock use and ethanol productivity fixed, the next step is to determine whether ethanol
productivity is more profitable than electricity generation. Not all the gas is expected to be
consumed in the process. Simulation results will tell how much syngas is consumed exactly,
allowing a comparison between its energy content and the benefit from ethanol production.

7. SIMULATION RESULTS
7.1 Process flow diagram
Figure 12. Process flow diagram of ethanol synthesis by gas fermentation. Symbols used comply with Finnish standards [53].

7.2 Process description
Figure 12 illustrates the process flow diagram for the transformation of steel mill syngas into
ethanol by fermentation. As discussed, there are four main steps in the process: bacterial growth,
syngas pretreatment, fermentation, and product separation.
30 % of the syngas being generated in the steel mill is taken to the plant: 429,1 kmol/h of syngas
at 30 °C and 1 bar with a molar composition of 86 % CO, 4 % H2, 5 % CO2 and 5 % N2 (stream
1). The gas is compressed in C-101 to 3,8 bars to enhance mass transfer in the bioreactor and
increase ethanol productivity. Compression raises the temperature of the gas to 219,2 °C, so the
gas is cooled down to 37 °C in E-101 in order to restore adequate temperature for the bacteria to
thrive. After cooling, the gas is sparged in airlift reactor R-101, where fermentation takes place.
The bacteria is fed to the reactor in stream 11. Cell concentration in the stream is 155 kg/m 3.
Since residence time in the reactor is adjusted to the life spam of bacteria (77 hours), 233,4 kg/h
of bacteria are carried in the stream, together with 1,5 m3/h of water. Bacteria are grown in
stirred vessel V-101, which is fed by 23,3 kg/h of Clostridium L. (stream 7), 210 kg/h of ATCC
nutrient medium 1754 (stream 8), and 1,5 m3/h of water (stream 9). Temperature in the vessel is
kept at 37 °C, while residence time is the growth time: 36 hours. The bacteria and water are
removed from the vessel in stream 10, which is pumped to airlift reactor by pump P-102. The
rest of the water needed in R-101 is supplied by stream 5, which carries 9,7 m3/h of water. 85%
of the water in stream 5 comes from recycle stream 23, so 4 kmol/h of acetic acid are present in
the flow. The stream is pumped to reactor R-101 by P-101.
Streams 3, 6, and 11 containing syngas, water, and bacteria respectively are fed to airlift reactor R-
101, which is kept at optimal conditions for C. Ljungdahlii to carry out fermentation: 37 °C and
pH level of 6. Gas enters the reactor at 3,8 bar, and loses pressure as it raises and dissolves in the
liquid medium. Unreacted gases leave the reactor from the top at atmospheric pressure in stream
12, which contains 389,2 kmol/h of syngas with a molar composition of 76,9 % CO, 1,4 % H2,
16,2 % CO2 and 5,5 % N2. Cell concentration in R-101 is maintained at 20 kg/m3, while ethanol
concentration is closely monitored to avoid surpassing 5 % concentration in volume, above which
the bacteria cannot survive. The fermentation broth is removed as stream 13 at the same rate at
which the liquid feed is supplied: 587,3 kmol/h with a molar composition of 97 % water, 2,1%
ethanol, and 0,9 % acetic acid.
Stream 13 at 37 °C is used to cool down stream 20 coming from the bottom of the distillation
column at 106,4 °C, which serves as a recycle stream due to its high content in water (99,1 %
mol). Heat exchange takes place in E-102, after which the fermentation broth temperature is
raised to 99 °C. Pump P-103 is then used to pump the stream into distillation column T-101,
where products are separated according to their relative volatilities.
Stream 15 containing 587,3 kmol/h of fermentation broth enters distillation column T-101 at
99 °C and 2,4 bar in stage 22 (above-stage convention). Total number of plates is 25 and
condenser is total. Pressure at the top is atmospheric, while pressure drop per stage is 0,7 kPa.
Reflux ratio is 17, and distillate leaves the column as stream 16 containing 19 kmol/h of water
and ethanol in a molar composition of 33 and 67 %, respectively. Bottom product leaves the
column at a rate of 568,3 kmol/h and a temperature of 106.4 °C. It contains water (99,1 % mol),
acetic acid (0,9 % mol) and all of the bacteria (233,4 kg/h).
Before recirculating the water back to the reactor, the dead bacteria are removed by means of
microfiltration. Bottom products from T-101 are pumped by P-104 before filtration in membrane
unit F-101. The membranes, made of PVC, operate with a transmembrane pressure of 1 bar and
remove all of the bacteria, including 5 % of the liquid stream: 0,6 m3/h. The concentrate (stream
19) is taken to a waste water treatment plant, while the permeate (stream 20) is cooled down
from 106,4 °C to 38 °C with stream 13 in heat exchanger E-102 as mentioned. In order to avoid
the buildup of acetic acid in the reactor, 20 % of stream 20 is bled before recycling and taken to a
waste water treatment plant together with stream 19. Finally, the recirculation stream is mixed
with stream 4 containing 1,6 m3/h of fresh water before being fed to the reactor.

7.3 Simulation diagram
Figure 13. Aspen Plus® simulation diagram.

7.4 Stream results
Through the use of Aspen Plus® v.8.6, stream results are obtained and saved. Input and output
stream specifications to the overall process are shown in Table 8.
Table 8. Input and output stream specifications to the overall process.
INPUT OUTPUT
Syngas Water Bacteria Nutrients Water Gas Ethanol Waste
Stream 1 4 7 8 9 12 16 19 22
Molar flow
429,06 87,79 - - 83,10 389,32 19 28,99 107,87
(kmol/h)
Mass flow
11915,33 1581,49 23,40 210,04 1497,12 11775,30 699,48 766,94 1985,60
(kg/h)
CO₂: 0,05 CO₂: 0,162
Composition H2O:0,991 H2O:0,991
H2:0,04 H2:0,014 H2O:0,33
(molar H2O:1 Bacteria:1 Nutrients:1 H2O:1 Ac. Ac.
CO:0,86 CO: 0,769 Eth.:0,67
fraction) acid:0,009 acid:0,001
N2:0,05 N2: 0,055
Temperature
30 37 37 37 37 37 78,43 106,47 38
(°C)
Pressure
1 1 - - 1 1 1 3,76 1,261
(bar)
Vapor
1 0 0 0 0 1 0 0 0
fraction
Liquid
0 1 0 0 1 0 1 1 1
fraction
Solid
0 0 1 1 0 0 0 0 0
fraction
Enthalpy
-13657,3 -6949,6 - - -6580,2 -16060,9 -1448,6 -2267,1 -8591,9
Flow (kW)
Global mass and energy balances for the process can be calculated from the values displayed in
Table 8. The results are the following:
Table 9. Global mass and energy balances.
OUTPUT-
Stream 1 4 7 8 9 12 16 19 22
INPUT
Molar flow
(kmol/h)
429,06 87,79 - - 83,10 389,32 19 28,99 107,87 -54,77
Mass flow
(kg/h)
11915,33 1581,49 23,40 210,04 1497,12 11775,30 699,48 766,94 1985,60 -0,05
Enthalpy -1181,4
-13657,3 -6949,6 - - -6580,2 -16060,9 -1448,6 -2267,1 -8591,9
flow (kW)
The negative energy balance implies that the process is generating energy in the form of heat,
allowing for the possibility of heat integration.

Detailed information for the main streams in the process is shown in the following table:
Table 10. Stream results.
Stream 1 2 3 4 5 6 7 8
Output eq. B6 C-101 E-101 B5 B4
Input eq. C-101 E-101 R-101 B5 B4 R-101 V-101 V-101
Phase Vapor Vapor Vapor Liquid Liquid Liquid Solid Solid

Mole flow (kmol/hr)
CO₂ 21,45 21,45 21,45 0 0 0 0 0
CO 369 369 369 0 0 0 0 0
H₂ 17,16 17,16 17,16 0 0 0 0 0
H2O 0 0 0 87,79 515,24 515,24 0 0
Ethanol 0 0 0 0 0,02 0,02 0 0
Acetic acid 0 0 0 0 4,01 4,01 0 0
N₂ 21,45 21,45 21,45 0 0 0 0 0
Mole Fraction
CO₂ 0,050 0,050 0,050 0 0 0 - -
CO 0,860 0,860 0,860 0 0 0 - -
H₂ 0,040 0,040 0,040 0 0 0 - -
H2O 0 0 0 1 0,992 0,992 - -
Ethanol 0 0 0 0 0 0 - -
Acetic acid 0 0 0 0 0,008 0,008 - -
N₂ 0,050 0,050 0,050 0 0 0 - -
Mass flow (kg/hr)
Clostridium L. 0 0 0 0 0 0 23,4 0
Nutrients 0 0 0 0 0 0 0 210,04
CO₂ 944,01 944,01 944,01 0 0 0 0 0
CO 10335,84 10335,84 10335,84 0 0 0 0 0
H₂ 34,59 34,59 34,59 0 0 0 0 0
H2O 0 0 0 1581,49 9282,11 9282,11 0 0
Ethanol 0 0 0 0 0,71 0,71 0 0
Acetic acid 0 0 0 0 241,06 241,06 0 0
N₂ 600,89 600,89 600,89 0 0 0 0 0
Mass fraction
Clostridium L. 0 0 0 0 0 0 1 0
Nutrients 0 0 0 0 0 0 0 1
CO₂ 0,079 0,079 0,079 0 0 0 - -
CO 0,867 0,867 0,867 0 0 0 - -
H₂ 0,003 0,003 0,003 0 0 0 - -
H2O 0 0 0 1 0,975 0,975 - -
Ethanol 0 0 0 0 0 0 - -
Acetic acid 0 0 0 0 0,025 0,025 - -
N₂ 0,050 0,050 0,050 0 0 0 - -
Mole flow (kmol/hr) 429,06 429,06 429,06 87,79 519,26 519,26 0 0
Mass flow (kg/hr) 11915,33 11915,33 11915,33 1581,49 9523,87 9523,87 23,4 210,04
Volume Flow (m³/hr) 10809,20 4627,68 2897,56 1,60 9,71 9,71 0 0
Temperature (°C) 30 219,24 37 37 37,49 37,53 37 37
Pressure (bar) 1 3,8 3,8 1 1 2 - -
Vapor Fraction 1 1 1 0 0 0 0 0
Liquid Fraction 0 0 0 1 1 1 0 0
Molar Enthalpy (kJ/mol) -114,6 -108,9 -114,4 -285,0 -286,5 -286,5 - -
Enthalpy Flow (kJ/s) -13657,3 -12981,9 -13638,7 -6949,6 -41321,2 -41320,5 - -

Stream 9 10 11 12 13 14 15 16
Output eq. V-101 B3 B2 B2 E-102 B8 T-101
Input eq. V-101 B3 R-101 E-102 B8 T-101
Phase Liquid Liquid Liquid Vapor Liquid Liquid Liquid Liquid

Mole flow (kmol/hr)
CO₂ 0 0 0 63,23 0 0 0 0
CO 0 0 0 299,20 0 0 0 0
H₂ 0 0 0 5,44 0 0 0 0
H2O 83,10 83,10 83,10 0 569,29 569,29 569,29 6,27
Ethanol 0 0 0 0 12,75 12,75 12,75 12,73
Acetic acid 0 0 0 0 5,29 5,29 5,29 0
N₂ 0 0 0 21,45 0 0 0 0
Mole Fraction
CO₂ 0 0 0 0,162 0 0 0 0
CO 0 0 0 0,769 0 0 0 0
H₂ 0 0 0 0,014 0 0 0 0
H2O 1 1 1 0 0,969 0,969 0,969 0,330
Ethanol 0 0 0 0 0,022 0,022 0,022 0,670
Acetic acid 0 0 0 0 0,009 0,009 0,009 0
N₂ 0 0 0 0,055 0 0 0 0
Mass flow (kg/hr)
Clostridium L. 0 233,4 233,4 0 233,4 233,4 233,4 0
Nutrients 0 0 0 0 0 0 0 0
CO₂ 0 0 0 2782,794 0 0 0 0
CO 0 0 0 8380,622 0 0 0 0
H₂ 0 0 0 10,97599 0 0 0 0
H2O 1497,12 1497,12 1497,12 0 10255,99 10255,99 10255,99 112,91
Ethanol 0 0 0 0 587,50 587,50 587,50 586,57
Acetic acid 0 0 0 0 317,54 317,54 317,54 0
N₂ 0 0 0 600,89 0 0 0 0
Mass fraction
Clostridium L. 0 0,135 0,135 0,000 0,020 0,020 0,020 0
Nutrients 0 0 0 0 0 0 0 0
CO₂ 0 0 0 0,236 0 0 0 0
CO 0 0 0 0,712 0 0 0 0
H₂ 0 0 0 0,001 0 0 0 0
H2O 1 0,865 0,865 0 0,900 0,900 0,900 0,161
Ethanol 0 0 0 0 0,052 0,052 0,052 0,839
Acetic acid 0 0 0 0 0,028 0,028 0,028 0
N₂ 0 0 0 0,051 0 0 0 0
Mole flow (kmol/hr) 83,10 83,10 83,10 389,32 587,33 587,33 587,33 19
Mass flow (kg/hr) 1497,12 1730,52 1730,52 11775,30 11394,40 11394,40 11394,40 699,48
Volume Flow (m³/hr) 1,52 1,52 1,52 4174,88 11,52 12,35 12,35 0,92
Temperature (°C) 37 37 37,06 37 37 99,03 99,05 78,43
Pressure (bar) 1 1 2 1 2,4 1,9 2,4 1
Vapor Fraction 0 0 0 1 0 0 0 0
Liquid Fraction 1 1 1 0 1 1 1 1
Molar Enthalpy (kJ/mol) -285,1 -285,1 -285,0 -148,5 -286,6 -281,9 -281,9 -274,5
Enthalpy Flow (kJ/s) -6580,2 -6580,2 -6580,1 -16060,9 -46763,0 -45990,0 -45989,6 -1448,6

Stream 17 18 19 20 21 22 23
Output eq. T-101 B9 B7 B7 E-102 B1 B1
Input eq. B9 B7 E-102 B1 B5
Phase Liquid Liquid Liquid Liquid Liquid Liquid Liquid

Mole flow (kmol/hr)
CO₂ 0 0 0 0,00 0 0 0
CO 0 0 0 0,00 0 0 0
H₂ 0 0 0 0,00 0 0 0
H2O 563,03 563,03 28,71 534,312 534,31 106,86 427,45
Ethanol 0,0202403 0,0202403 0,00103226 0,0192077 0,02 0,00 0,02
Acetic acid 5,287752 5,287752 0,2696754 5,017584 5,02 1,00 4,01
N₂ 0 0 0 0 0 0 0
Mole Fraction
CO₂ 0 0 0 0,000 0 0 0
CO 0 0 0 0,000 0 0 0
H₂ 0 0 0 0,000 0 0 0
H2O 0,9906606 0,9906606 0,99066036 0,9906613 0,991 0,991 0,991
Ethanol 0 0 0 0 0,000 0,000 0,000
Acetic acid 0,00930395 0,00930395 0,00930395 0,009303 0,009 0,009 0,009
N₂ 0 0 0 0,000 0 0 0
Mass flow (kg/hr)
Clostridium L. 233,4 233,4 233,4 0 0 0 0
Nutrients 0 0 0 0 0 0 0
CO₂ 0 0 0 0 0 0 0
CO 0 0 0 0 0 0 0
H₂ 0 0 0 0 0 0 0
H2O 10143,08 10143,08 517,30 9625,781 9625,78 1925,16 7700,62
Ethanol 0,9324554 0,9324554 0,0475552 0,8848836 0,88 0,18 0,71
Acetic acid 317,543 317,543 16,1947 301,3188 301,32 60,26 241,06
N₂ 0 0 0 0,00 0 0 0
Mass fraction
Clostridium L. 0,02182328 0,022 0,304 0,000 0,000 0,000 0,000
Nutrients 0 0 0 0 0 0 0
CO₂ 0 0 0 0,000 0 0 0
CO 0 0 0 0,000 0 0 0
H₂ 0 0 0 0,000 0 0 0
H2O 0,94839458 0,948 0,674 0,9695609 0,970 0,970 0,970
Ethanol 8,7186E-05 8,7186E-05 6,2006E-05 8,913E-05 0,000 0,000 0,000
Acetic acid 0,02969079 0,02969079 0,02111602 0,0303505 0,030 0,030 0,030
N₂ 0 0 0 0,000 0 0 0
Mole flow (kmol/hr) 568,33 568,33 28,99 539,35 539,35 107,87 431,48
Mass flow (kg/hr) 10695,00 10695,00 766,94 9927,98 9927,98 1985,60 7942,39
Volume Flow (m³/hr) 11,51 11,51 0,59 10,92 10,13 2,03 8,11
Temperature (°C) 106,3718 106,4743 106,4743 106,4743 38 38 38,00
Pressure (bar) 1,261 3,761 3,761 3,761 3,761 3,761 3,761
Vapor Fraction 0 0 0 0 0 0 0
Liquid Fraction 1 1 1 1 1 1 1
Molar Enthalpy (kJ/mol) -281,6 -281,6 -281,6 -281,6 -286,7 -286,7 -286,7
Enthalpy Flow (kJ/s) -44455,5 -44453,7 -2267,1 -42186,5 -42959,6 -8591,9 -34367,7

7.5 Equipment results
Simulation results allow for further specification of the equipment. Equipment specification is
necessary in order to develop a preliminary economic evaluation of the project. The results have
been saved and displayed.
Airlift reactor R-101
Reactor conditions and design specifications have already been explained in “Process overview
and design”. Simulation results obtained for reactor R-101 are displayed below:
587,3 kmol/h
H2O: 0,969
Ac. acid: 0,009
Ethanol: 0,022_
Bacteria: 233 kg/h
37 °C
2,4 bar
602,36 kmol/h
H2O: 0,993
Ac. acid: 0,006
Ethanol: 0,001_
Bacteria: 233 kg/h
37 °C
1 bar
Table 11. Reactor results summary.
All reactions that take place in the reactor are exothermic. As a result, large amounts of heat are
being generated in the reactor: up to 1153 kW. Proper cooling with water is necessary in order to
maintain the temperature constant. The removed heat can then be used in other parts of the
process such as, for example, the boiler in distillation column T-101.
Mass, mole, and energy balances for reactor R-101 are also calculated by Aspen Plus®. Results
are displayed in the following table:
Table 12. Mass, mole, and energy balances for reactor R-101.
Distillation column T-101

As explained in “Methodology”, distillation column design in Aspen Plus® is made based on the
results from the Fenske-Underwood equations for multicomponent distillation. These results, as
well as the rules of thumb proposed by Seader and Henley are used to specify inputs for the
DSTWU block, in order to obtain a rough estimation of results that yield 84 % purity in mass of
ethanol in the distillate.
Heavy and light key components are, respectively, water and ethanol. Input values to the
DSTWU block include: condenser specifications, light and heavy key component recoveries,
condenser and boiler pressures and reflux ratio. Reflux ratio is fixed at 1,3 (in Aspen Plus® it is
specified with a negative symbol –1,3), condenser is total, light and heavy key component
recoveries are 0,9986 and 0,011, respectively, and condenser and boiler pressures at 1 bar. All of

these are the results obtained by the previously mentioned equations and rules of thumb. These
inputs and the results of simulation are shown in Table 13.
Table 13. Input values and results from DSTWU block.
The results obtained from the DSTWU model are then used as input values in the more rigorous
RADFRAC distillation column block. However, results show that the purity of ethanol in the
distillate does not meet the 84 % in mass target. After adjustments in the number of stages, reflux
ratio and the feed stage, the target is met. Total number of stages is 25 and reflux ratio is 18.
Feed stage is 22 (above-stage convention) and condenser is total. Pressure in the condenser is set
as 1 bar, with 10 and 0,7 kPa pressure drops in the condenser and each stage, respectively. The
input values and the results are illustrated in Tables 14 through 16:
Table 14. . Adjusted input values in RADFRAC column model for T-101.

Table 15. Equipment specifications for T-101. Table 16. Split fraction results for T-101
Condenser/top stage performance

Temperature 78,4 °C
Heat duty -3,81 MW
Distillate rate 19 kmol/h
Reflux rate 323 kmol/h
Reflux ratio 17
Reboiler/bottom stage performance
Temperature 106,4 °C
Heat duty 3,89 MW
Bottoms rate 568,3 kmol/h
Boilup rate 346,2 kmol/h
Boilup ratio 0,61
Compressor C-101
Compressor C-101 is used to raise the pressure of the syngas in order to increase mass transfer
rates in the bioreactor. Input specifications and results are explained in the following tables:
Table 17. Compressor C-101 input values.
Table 18. Compressor C-101 results.

Heat exchangers
After compression in C-101, syngas temperature is raised to 219 °C. In order to maintain a
constant pressure in the reactor, the gas needs to be cooled down to 37 °C in E-101. Cold water
is used as cooling fluid in this equipment. Cooler E-101 is shell and tube type, and since
geometrical specifications are unknown, shortcut countercurrent model has been selected. Input
specifications and results for E-101 are shown in Tables 19 and 20:
Table 19. Input specifications for cooler E-101.
Table 20.Cooler E-101 results.

Heat exchanger E-102 is used to cool down the water recycle stream from 106,4 to 38 °C. The
stream used to provide cooling is the fermentation broth coming out of the bioreactor, which is
heated from 37 to 99 °C. Heat exchanger E-102 is shell and tube type, and since geometrical
specifications are unknown, shortcut countercurrent model has been selected. Pressure drop is
estimated at 50 kPa [53]. Input specifications and results are shown in the following tables:
Table 21. Input specifications for heat exchanger E-102.
Table 22. Heat exchanger E-102 results.

Pumps
A total of four pumps are used in the process to move liquid streams from one equipment to
another. Pumps are used to overcome pressure loss in pipes and equipment such as heat
exchangers or membranes. Since equipment and piping geometric specifications have not been
developed, pressure losses are only estimations based on rules of thumb from Markku Hurme’s
Process Design Manual [53]. Pump specifications and results are displayed in the following
tables:
Table 23. Input values for pumps.
Outlet pressure/pressure increase in pumps

P-101 2 bar
P-102 2 bar Discharge pressure
P-103 2 bar
P-104 2,5 bar Pressure increase
Table 24. Pump results. From left to right, top to bottom: P-101, P-102, P-103, P-104.

8. PROCESS CONTROL
Process conditions have been defined and explained. These variables must be kept constant in
order to maximize efficiency and, most importantly, ensure the safety of the process. Process
control allows to meet this objective. The design of the control of an engineering plant includes a
study of the free variables to control in each unit operation and a P&ID diagram which illustrates
the instruments used to monitor and manipulate these variables. A rough design of the control of
the bacterial growth, gas pretreatment, and fermentation operations is presented in this project.
P&ID diagram for this process is shown in Figure 14.
Bacterial growth
One of the most important variables in the growth of bacteria is the temperature. Bacteria must
be kept at a constant temperature of 37 °C in order to create a friendly environment in which they
are able to grow. Temperature is closely monitored and, depending on its fluctuation, cooling
water input is increased or decreased to compensate variations.
The process also depends heavily on the quantity of nutrients and bacteria being fed to the tank,
which are also controlled. In order to maintain a residence time of 36 hours that allow the
bacteria to grow properly, the liquid level is regulated with the input flow of water. Finally, the
capacity of production of the process depends on the amount of bacteria that is being fed to the
bioreactor: 233,4 kg/h. With bacteria and nutrient inflows and the level of the tank already
controlled, the production capacity is regulated at the exit of the tank with a control of the flow,
which is fixed at 1,52 m3/h.
Gas pretreatment
As discussed earlier, the production capacity is also heavily dependent on the pressure of the gas.
Pressure of the gas is controlled by modifying the spinning speed of the engine in the compressor.
Temperature before entering the bioreactor must also be kept at 37 °C, which is achieved by
modifying the cold water input in cooler E-101.
Fermentation
Temperature in the fermentation process is again an essential variable to optimize ethanol yields.
Given the size of the reactor, three different measurements are taken for the temperature at
different heights. The mean of these measurements is then compared to the setpoint value (37 °C)
in order to increase or decrease the input flow of cold water into the reactor jacket.
On the other hand, the flow of the water stream coming from recycling is regulated with two
controllers (FIC 3 and 4). FT 2 measures the flow of the recycling stream and takes it to FIC 4,
which fixes the bleed at 20 % of its flow. The same measurement is also taken to FIC 3 so that

fresh water can be added to compensate the losses. At this point the flows of the liquid feeds of
the reactor are fixed.
Gases leave the reactor at atmospheric pressure. However, the column is not open to the
atmosphere since these gases are reutilized for electricity generation. This is why pressure in the
top of the reactor is controlled by a valve in the vent gas stream.
Finally, the level within the tank is also controlled in order to ensure the residence time is fixed
at 77 hours (life spam of the bacteria), complying as well with the 5 % concentration limit of
ethanol in the bioreactor. Since the bioreactor is a bubble column, level measurements could be
deceptive, so the liquid level is rather controlled with a measurement of the hydrostatic pressure
at the bottom, which regulates the outflow of fermentation broth that is taken to distillation.

Figure 14. P&ID for bacterial growth, gas pretreatment and fermentation.

9. WASTE TREATMENT AND ENVIRONMENTAL IMPACT
Carbon capture and reuse from waste gases to make fuel ethanol has a beneficial impact on the
environment, as it reduces greenhouse gas emissions. The European Union has declared second
generation biofuels such as ethanol made from the steel mill flue gases to be the fastest and most
cost efficient way to meet the goals of the Paris Agreement, and as a result substantial economic
incentives are given to boost this industry.
The results from the simulation show that the carbon balance between input and output of gas is
negative, meaning that carbon is indeed captured into ethanol and acetic acid molecules. These
results are illustrated in Table 25, where gas inlet and outlet streams as well as consumption are
specified:
Table 25. Input, output and consumption of gas in the bioreactor.
INPUT OUTPUT CONSUMED

Molar flow (kmol/h) 429,06 389,32 36,74
CO 369 299,2 69,8
H2 17,2 5,4 11,8
CO2 21,5 63,2 -41,7
N2 21,5 21,5 0
As seen in Table 25, both carbon monoxide and hydrogen gas are consumed, whereas carbon
dioxide is produced. This is due to the fact that reactions that yield ethanol also produce CO2,
and they take place as much as 10 times more than the reactions that yield acetic acid, which
consume CO2.
The production of carbon dioxide could be deceptive since it could falsely be concluded that
greenhouse gases are produced in the process instead of being consumed. Nevertheless, the
carbon balance proves negative, since more CO is consumed than CO2: as much as 18,1 kmol/h,
or 1737 tons per year of carbon. The use of the steel mill flue gases to produce ethanol is thus
more beneficial than its current use, in which carbon monoxide is flared to produce electricity
and transformed into carbon dioxide, which is emitted into the atmosphere. In addition, the
environmental impact of the process is further reduced by recycling most of the water used in the
process.
9.1 Waste management.
The waste streams in the process are three:

 Gas leaving the reactor.
 Retentate from the membrane unit containing the bacteria.
 Bleed from the recirculation of water.
The gas will not be treated as waste since it is used to produce electricity in the plant. The
possibility of using it to increase productivity by introducing it in a second reactor in series could
also be studied, but it will not be discussed here.
According to the Industrial Emissions Directive 2010/75 EU, the list of pollutants to consider in
waste water streams is the following [54]:
1. Organohalogen compounds and substances which may form such compounds in the aquatic
environment
2. Organophosphorus compounds
3. Organotin compounds
4. Substances and mixtures which have been proved to possess carcinogenic or mutagenic
properties or properties which may affect reproduction in or via the aquatic environment
5. Persistent hydrocarbons and persistent and bioaccumulable organic toxic substances
6. Cyanides
7. Metals and their compounds
8. Arsenic and its compounds
9. Biocides and plant protection products
10. Materials in suspension
11. Substances which contribute to eutrophication (in particular, nitrates and phosphates)
12. Substances which have an unfavourable influence on the oxygen balance (and can be
measured using parameters such as BOD, COD, etc.)
13. Substances listed in Annex X to Directive 2000/60/EC

Waste waters from the membrane unit contain acetic acid and bacteria, whereas the purge
contains only acetic acid. Acetic acid is present in both water streams in a concentration of 3 %
w/w, whereas the bacteria is removed at a rate of 233,4 kg/h.
One simple and cost-effective solution to remove the bacteria from the waste water coming from
the membrane filtration unit would be to use a drier. Dried bacteria could then be used as animal
feed. The separation of acetic acid, on the other hand, requires techniques such as ultrafiltration,
pervaporation, or electrodyalisis. Other methods such as azeotropic or reactive distillation are not
feasible given the low concentrations in which the acetic acid is present.
Another possibility worth studying would be to use the same membrane unit to separate both the
acetic acid and the bacteria from the water. This could be achieved, for example, with a
ultrafiltration membrane or through reverse osmosis. The water would then be recirculated
without the need of a purge, whereas the bacteria and the acetic acid in the retentate could be
then separated through the use of a drier.

10. SAFETY
Ensuring the safety of the process is a crucial step in the design of the plant. Safety
considerations and precautions have been gathered concerning chemicals involved in the process
that may suppose a hazard to the operators.
10.1 Safety considerations for carbon monoxide
Carbon monoxide is an odorless, colorless, highly toxic and flammable gas.

Health hazards from exposure to carbon monoxide are:
 Headache, dizziness, vomiting, nausea, convulsions, rapid breathing, hallucinations and
confusion.
 If exposure is long enough, unconsciousness and death can happen.
 People who survive severe CO exposure may suffer long –term health problems.
Industrial handling of CO requires the following to prevent health hazards due to exposure:
 Product to be handled in a closed system and under strictly controlled conditions.
 Preferably use only permanent leak-tight installations (e.g. welded pipes).
 Systems under pressure should be regularly checked for leakages.
 Alarm detectors should be used when toxic gases may be released.
 Keep self-contained breathing apparatus readily available for emergency use.
 Consider the use of flame resistant anti-static safety clothing.
 Wear safety glasses with side shields.
 Handle in a well-ventilated atmosphere.
In order to prevent fire hazards, follow these precautionary measures:
 Keep away from ignition sources (including static discharges).
 Take precautionary measures against static discharge.
 Do not smoke while handling product.
 Assess the risk of potentially explosive atmosphere and the need for explosion-proof
equipment.
 All electrical equipment in the storage areas should be compatible with the risk of
potentially explosive atmosphere.
In case of fire, these are the instructions for firefighters:
 If possible, stop flow of product.
 Coordinate fire measure to the surrounding fire. Cool endangered containers with water
spray jet from a protected position. Do not empty contaminated fire water into drains.

 Do not extinguish a leaking gas flame unless absolutely necessary.

Spontaneous/explosive re-ignition may occur. Extinguish any other fire.
 Use self-contained breathing apparatus.
In the case of accidental release, the following must be done:
 Try to stop release, if possible.

 Evacuate area.
 Consider the risk of potentially explosive atmospheres.
 Eliminate ignition sources.
 Monitor concentration of released product.
 Ensure adequate air ventilation.
 Wear self-contained breathing apparatus when entering area unless atmosphere is proved
to be safe.
10.2 Safety considerations for carbon dioxide
Carbon dioxide is a colorless gas, odorless at low concentrations. All forms of carbon dioxide are
non-combustible. It is heavier than air and highly soluble in water.
Health hazards from exposure to carbon monoxide are, from lower to higher concentration levels:
 1%: slight increase in breathing rate.

 2%: breathing rate increases to 50 % above normal levels. Headaches and tiredness.
 3%: breathing increases to twice the normal rate. Weak narcotic effect. Impaired hearing,
headaches, increased blood pressure.
 4-5%: breathing increases to 4 times the normal rate. Symptoms of intoxication become
evident and slight choking may be felt.
 5-10%: Very labored breathing, headache, visual impairment and ringing of ears. Judgment
may be impaired, followed by unconsciousness.
 50-100%: death, asphyxiation.
Industrial handling of CO2 requires the following to prevent health hazards due to exposure:
 Be aware of any signs of dizziness, fatigue, or any of the exposure symptoms described
above.
 Use adequate ventilation.
 Wear safety glasses with side shields.
 Concentration levels should be monitored with detectors to warn operators when levels
become hazardous.

 If exposure takes place, remove victims to fresh air as soon as possible. Trained personnel to
administer supplemental oxygen or cardio-pulmonary resuscitation, if necessary.

Carbon dioxide is non-combustible, so no fire hazards apply. In fact, it is used as a fire-
extinguisher agent given that it is heavier than air. When controlling a blaze, use extinguishing
media appropriate for surrounding fire.

 Response must be coordinated by pre-planned procedures and trained personnel.
 Proper protective equipment should be used.
 In case of spill, clear affected area and evacuate the people.
 Minimum personal protective equipment should be: protective clothing, self-contained
breathing apparatus.
 Locate and seal the source of the leaking gas.
 Allow the gas, which is heavier than air, to dissipate.
 Monitor CO2 levels before allowing any personnel to go back in the area.
10.3 Safety considerations for hydrogen gas
Hydrogen gas is colorless and non-toxic. It is highly flammable with most oxidizing gases. It
also presents an auto ignition temperature between 500 and 570 °C.
Health hazards from exposure to hydrogen gas are:

 High concentrations of hydrogen so as to exclude an adequate supply of oxygen to the lungs
cause dizziness, labored breathing, possible nausea and eventual unconsciousness.
 Hydrogen gas may result fatal if inhaled in for prolonged periods.
 The eyes can be injured by exposure to the cold gas that would otherwise be too brief to
affect the skin.
 Contact with the liquid or cold gas can produce severe cryogenic burns.
 Hydrogen is defined as a simple asphyxiant. Oxygen levels should be maintained at greater
than 18 molar % at normal atmospheric pressure which is equivalent to a partial pressure of
135 mm Hg.
Industrial handling of H2 requires the following to prevent health hazards due to exposure:
 Use adequate ventilation.

 Concentration levels should monitored with detectors to warn operators when levels become
hazardous.
 Approach suspected leak area with caution.
 Wear respiratory protection.
 Use a back flow preventative device in the piping.
 If inhaled, get medical attention immediately. Call a poison center or physician. Remove
victim to fresh air and keep at rest in a position comfortable for breathing. If it is suspected
that fumes are still present, the rescuer should wear an appropriate mask or self-contained
breathing apparatus.
 If not breathing, if breathing is irregular or if respiratory arrest occurs, provide artificial
respiration or oxygen by trained personnel. It may be dangerous to the person providing aid
to give mouth-to-mouth resuscitation.

 Use explosion-proof ventilation equipment.
 Keep away from heat, hot surfaces, sparks, open flames and other ignition sources.
 No smoking.
 Use explosion-proof electrical (ventilating, lighting and material handling) equipment.
 Preferably use only permanent leak-tight installations (e.g. welded pipes).

 In a fire or if heated, a pressure increase will occur and the container may burst, with the risk
of a subsequent explosion.
 Decomposition products may include sulfur oxides.
 Promptly isolate the scene by removing all persons from the vicinity of the incident if there is
a fire.
 Use water spray to keep fire-exposed containers cool.
 If involved in fire, shut off flow immediately if it can be done without risk. If this is
impossible, withdraw from area and allow fire to burn.
 Fight fire from protected location or maximum possible distance.
 Eliminate all ignition sources if safe to do so.
 Fire-fighters should wear appropriate protective equipment and self-contained breathing
apparatus (SCBA) with a full face-piece operated in positive pressure mode.

 Accidental releases pose a serious fire or explosion hazard. No action shall be taken
involving any personal risk or without suitable training.

 Evacuate surrounding areas. Keep unnecessary and unprotected personnel from entering.
 Shut off all ignition sources.
 No flares, smoking or flames in hazard area. Do not breathe gas. Provide adequate ventilation.
 Wear appropriate respirator when ventilation is inadequate.
 Put on appropriate personal protective equipment.
 Use spark-proof tools and explosion-proof equipment.
10.4 Safety considerations for ethanol
Ethanol is a volatile, flammable, colorless liquid with a slight characteristic odor.
Health hazards from exposure to ethanol are:
 Serious eye irritation with possible corneal injury.

 Symptoms may include dizziness, headache, nausea and loss of co-ordination. Inhalation
may affect the nervous system causing headache, possibly dizziness, nausea, weakness, loss
of coordination and unconsciousness.
 Slightly irritant to the skin.
Industrial handling of ethanol requires the following to prevent health hazards due to exposure:
 Remove victim to fresh air and keep at rest in a position comfortable for breathing.
 After contact with skin, take off immediately all contaminated clothing, and wash
immediately with plenty of water and soap. Clean contaminated surfaces with an excess of
water. If medical advice is needed, have product container or label at hand.
 In case of contact with eyes, rinse immediately with plenty of flowing water for 10 to 15
minutes holding eyelids apart. Subsequently consult an ophthalmologist.
 Do not induce vomiting. If accidentally swallowed rinse the mouth with plenty of water (only
if the person is conscious) and obtain immediate medical attention.
 Ensure the grounding of containers, apparatus, pumps and suction equipment.
 Use only in well-ventilated areas. If that’s not the case, use proper respiratory protection.
 Use personal protective equipment as required: PVC protective globes, tightly fitted safety
goggles, rubber apron.

 Keep away from sources of ignition.
 No smoking.
 Vapours can travel considerable distances to a source of ignition where they can ignite, flash
back, or explode.

 Avoid contact with oxidizers.
 Cool tanks/drums with water spray/remove them into safety.

 Wear self-contained breathing apparatus.
 Emergency cooling must be provided for in case of fire.
 Remove product from area of fire.

 Stop leak if safe to do so. Remove all sources of ignition.
 Evacuate unnecessary personnel.
 No flares, smoking or flames in hazard area.
 Wear appropriate respirator when ventilation is inadequate.
 Put on appropriate personal protective equipment.
 Use spark-proof tools and explosion-proof equipment.

11. ECONOMIC ANALYSIS
The equipment needed in the process has been roughly specified, allowing to make a first
approach on the economic viability of the project. The analysis is made based on the idea that
once the equipment costs are known, capital investment can be calculated through a series of
rules of thumb that determine installation, construction, and contingency costs. On the other hand,
information about utilities and raw materials has also been calculated, so operation costs can be
estimated. The capacity of production will determine the gross benefit as well as the return of
investment and net present value. A sensitivity analysis is also presented in order to support the
validity of the estimations made in terms of product price, which is very volatile, and other
contributors to the project cost. Finally, in order to justify the execution of the project, the profit
obtained from ethanol production is compared to the profit currently obtained from the
generation of electricity from the same amount of gas.
11.1 Capital cost estimation
All the costs for the equipment except airlift reactor R-101, membrane filtration unit F-101,
cooler E-101 and heat exchanger E-102 have been estimated using equations and cost curves
found in Towler and Sinnot’s Chemical Engineering Design Manual [55] and Timmerhaus’s
Plant Design Economics for Chemical Engineers [56]. These equations rely on different
parameters depending on the type of equipment. The costs have been updated using the
corresponding cost indexes (CEPCI) for the year in which the book was published: 395,6 for
2002 and 532,9 for 2010. The CEPCI value for 2016 is 544,9. Outotec® and Microdyn®
provided the price for the airlift reactor and the membrane filtration unit, respectively, whereas
the cost of the cooler and heat exchanger were estimated using a website by the name of
Matche.com [57]. Storage tank S-101 has been added to take into account the storage of the final
product: ethanol.
The costs of installation are determined by percentage of purchased equipment cost [56]. The
installation cost of equipment includes labor, foundations, supports, platforms, cost of
construction and all other factors which are relevant to the assembling of equipment. All
equipment are built using stainless steel. In addition, the phases in the process are liquid and gas,
whereas pressures are always under 4 bar and temperatures vary from 220°C to 25 °C. Table 26
shows a summary of purchase and installation costs for each equipment according to these
conditions.

Table 26. Purchased equipment and total cost after installation of main equipment.
Purchased equipment Price (€) Installation cost Total cost (€)

(%)
1. Agitated vessel V-101 67459,2 30 % 87697,0

2. Pump P-101 8231,4 25 % 10289,2
3. Pump P-102 8291,7 25 % 10364,6
5. Membrane filter F-101 52650 65 % 86872,5
6. Airlift reactor R-101 1400000 60 % 2240000,0
7. Distillation column T-101 175595,4 60 % 280952,7
9. Cooler E-101 29481,8 30 % 38326,3
10. Heat exchanger E-102 10305,1 30 % 13396,6
11. Pump P-103 8337,2 25 % 10421,5
12. Pump P-104 8290,8 25 % 10363,5
13. Storage tank S-101 52845,8 30 % 68699,5
14. Compressor C-101 294932,8 20 % 383412,7
Total 2116421,2 3240796,1
Total cost for the equipment including installation is roughly 3,25 million euros. This is known
as the inside battery limit (ISBL) cost. Outside battery limit (OSBL), supervision and
engineering and contingency costs are estimated at 30, 25, and 10 % of the ISBL cost,
respectively [55]. The sum of these costs constitutes the fixed capital investment. On the other
hand, start-up cost is estimated at 5 % of the fixed capital investment, resulting in a total capital
investment of 5,6 million euros. These values are explained in Table 27.
Table 27. Estimation of total capital investment.
Investment Cost (€)

ISBL 3240796,1
OSBL 972238,8
Engineering and supervision 810199,0
Contingency 324079,6
Total fixed capital investment 5347313,6
Working capital 267365,7
Total capital investment 5614679,3

11.2 Operation costs
Operation costs are divided into two categories: variable and fixed. Variable operation costs refer
to utilities, raw materials, waste water disposal and the cost of ethanol purification by an external
service. On the other hand, fixed operation costs include costs that are incurred regardless of the
operation rate: labor, supervision, maintenance… Costs are calculated on a yearly basis
considering an operational year has 8000 working hours.
11.2.1 Variable costs of operation
Raw materials used in the process include: water, bacteria and nutrients. Syngas is not
considered since it is obtained as a waste stream from the steel mill and it’s free. The annual
consumption and cost of the raw materials are summarized in the following table:
Table 28. Raw materials consumption and cost.
Consumption Annual cost

Raw materials Cost (€/kg)
(kg/h) (€/year)
Water 0,00162 [57] 3078,6 39898,8
Bacteria and nutrients 0,1 233,4 186752
Total 226650,8
The utilities used in the process are: electricity and cooling water. Electricity is consumed by the
pumps and, most importantly, by compressor C-101. The cost of electricity in the Finnish
industry is 50 €/MWh. Cooling utility is, in all cases, cooling water. Equipment that need cooling
are: cooler E-101, airlift reactor R-101, and the condenser in distillation column T-101. The
latter was in fact designed with Seader’s rules of thumb, which aim at the use of this utility in the
condenser given its availability and price. As for the boiler, medium pressure steam is used as a
heating utility. Cost of cooling water and medium pressure steam is 0,2 and 2 €/GJ, respectively
[58].

Tabla 29. Usage and cost of utilities.
Utility duty Utility usage Annual cost

Equipment Utility type (kW) (kg/h) (€/year)
P-101 Electricity 0,7 - 280
C-101 Electricity 675,5 - 270200

Cooling
E-101 -653,3 23953,8 754,3
water
Cooling
R-101 -1153 66201 2084,6
water
Cooling
Condenser T-101 -3810 218505,6 6880,4
water
Reboiler T-101 Steam 3890 6885,3 219156
Total electricity 678,5 - 271400

Total cooling
5616,3 308660,4 9719,3
water
Total steam 3890 218505,6 219156
Total utilities 500275,3
Other additional variable costs include the cost of ethanol purification and waste water disposal.
The final product for which the price is considered is fuel ethanol. As a result, the purification of
ethanol through an external service (e.g. ST1) must be considered. This cost is estimated as 5 %
of the retail price of fuel ethanol (616 €/ton). This reliability of this estimation will be tested in
the sensitivity analysis. On the other hand, The cost of disposing of the water that is bled from
the recirculation current is taken as 0,0022 €/kg [59].
Table 30. Annual cost for ethanol purification and waste water disposal.
Operation Cost (€/kg) Capacity (kg/h) Annual cost (€/year)
Ethanol purification 0,31 699,5 172356,8

Waste water disposal 0,0022 2519,14 44336,9
Total 216693,7

11.2.2 Fixed costs of operation
Given the size of the plant, a total of 2 operators per shift is sufficient. Being operational on a
continuous basis, 6 shift positions of 8 hours each are considered. The annual wage for each
operator is considered to be 41664 € [60]. On the other hand, supervision costs are estimated as
5 % of the operating labor, given the low supervision requirements in the plant. Side costs are set
at 150 % of the operating labor and supervision costs, as established by Mr. Koiranen (LUT).
Maintenance costs are 3 % of the ISBL since the plant handles mostly fluids [55]. Land fees are
not considered because the plant location is within the boundaries of Tornio’s steel mill.
Insurance is 1 % of ISBL and OSBL investments whereas depreciation is estimated to be 5 % of
the fixed capital investment, considering a life spam for the plant of 20 years. Quality control is
estimated as 0,5 % of the sales revenues. License fees and interest are set to be 2 % of the fixed
capital investment. Finally, corporate overhead charges, which include administrative, marketing,
and R&D costs, are estimated at 5 % of labor, supervision and maintenance, 2 % of total product
costs, and again 2 % of total product costs respectively. These costs are summarized in the
following table:
Tabla 31. Fixed operation cost estimation.
Annual cost
Fixed cost Correlation
(€/year)
Labor 6 shift positions 41664 €/year each 249984
Supervisions 5 % of operating labor 12499,2
150 % of operating labor and
Side costs and benefits 393724,8
supervisions
Maintenance 3 % of ISBL investment 97223,9
Insurance 1 % of ISBL and OSBL investment 42130,3
Quality control 0,5 % of sales revenues 15045,6
Interest 2 % of fixed capital investment 80209,7
License fees 2 % of fixed capital investment 80209,7
Depreciation 5 % of fixed capital investment 267365,7

5 % of labor, supervision, and
Administrative costs 17985,4
maintenance
Selling and marketing costs 2 % of total product costs 44000,0
Research and development
2 % of total product costs 44000,0
costs
Total fixed cost of
1344378,2
production

As seen in Figure 15, variable operation costs account for 41 % of the total costs of operation.
The biggest contributor to variable costs is utilities (22 %), followed by raw materials cost
(10 %), ethanol purification (7 %) and waste water treatment (2%). Fixed costs of production
account for the remaining 59 %, adding up altogether up to 2,3 million € in expenses.
Figure 15. Distribution of cost of manufacturing.
11.3 Revenue and profitability
Ethanol fuel price as of 2016 is 616 €/ton [61]. In order to analyze profitability, cash flow over
the life spam of the plant has been calculated. The life spam of the plant is considered to be 20
years, while construction is expected to take 1 year. Annual depreciation of the equipment is
calculated with a linear approach over the life spam of the plant, which is 5 % of the fixed capital
investment, as explained earlier. Annual production is calculated considering a 96 % purity of
fuel ethanol. The production capacity at the first year is set at 75 % due to expected difficulties,
and technical shutdowns scheduled every two years reduce the production capacity from 100 to
90 %. Taxes are not considered in this case given the uncertainty of the biofuel industry
regulations in the Finnish and EU markets with regards to tax exemptions. Working capital to
start up the plant is considered as 5 % of the fixed capital investment, but it is recovered in the
last year. Figure 16 shows the cash flow over the years, while detailed calculations are illustrated
in the next page.
10000000
8000000
6000000
4000000
Cash flow
2000000
0
0 5 10 15 20 25
-2000000
Year
-4000000
-6000000
-8000000
Figure 16. Cash flow over the plant’s life spam and construction.

Table 32. Cumulative cash flow over life spam and construction of the plant. Technical shutdown years are highlighted in grey.
Fixed capital Working Production Production Operation Cumulative

Year Depreciation Revenue Profit
investment capital capacity (kg/year) costs cash flow
1 5347314 267365,7 0 0% 0 0 0 0 -5614679
2 267365,7 75 % 3666056 1715999 2256846 540847,1 -5073832
3 267365,7 100 % 4888075 2287998 3009127 721129,4 -4352703
4 267365,7 90 % 4399268 2059198 2708215 649016,5 -3703686
5 267365,7 100 % 4888075 2287998 3009127 721129,4 -2982557
6 267365,7 100 % 4888075 2287998 3009127 721129,4 -2261427
7 267365,7 90 % 4399268 2059198 2708215 649016,5 -1612411
8 267365,7 100 % 4888075 2287998 3009127 721129,4 -891281
9 267365,7 100 % 4888075 2287998 3009127 721129,4 -170152
10 267365,7 90 % 4399268 2059198 2708215 649016,5 478864,6
11 267365,7 100 % 4888075 2287998 3009127 721129,4 1199994
12 267365,7 100 % 4888075 2287998 3009127 721129,4 1921123
13 267365,7 90 % 4399268 2059198 2708215 649016,5 2570140
14 267365,7 100 % 4888075 2287998 3009127 721129,4 3291269
15 267365,7 100 % 4888075 2287998 3009127 721129,4 4012399
16 267365,7 90 % 4399268 2059198 2708215 649016,5 4661415
17 267365,7 100 % 4888075 2287998 3009127 721129,4 5382545
18 267365,7 100 % 4888075 2287998 3009127 721129,4 6103674
19 267365,7 90 % 4399268 2059198 2708215 649016,5 6752691
20 267365,7 100 % 4888075 2287998 3009127 721129,4 7473820
21 267365,7 267365,7 100 % 4888075 2287998 3009127 721129,4 8194950

In order to determine the economic interest of the project, net present value has been used. The
net present value or NPV can be calculated from the cash flow in each year and the discount rate,
which is around 10 %. However, since the interest rate depends on several factors and is hard to
predict at this stage, the net present value has been calculated at different interest rates varying
from 6 to 14 %. As seen in Figure 17, negative NPV values are not reached even at high interest
rates, showing that even at these values the investment is profitable.
6000000
5000000
4000000
NPV (k€)
3000000
2000000
1000000
0
0.06 0.07 0.08 0.09 0.1 0.11 0.12 0.13 0.14 0.15
Interest rate
Figure 17. Net present value at different interest rates, varying from 6 to 14 %.
Other values that represent the economic interest of the venture have been calculated:
Table 33. Representative parameters of the economic interest of the project.
Parameter Value
Return on investment 12,3 %
Payback period 10 years
For a life spam of the plant of 20 years, a payback time of 10 years seems considerably high.
This
JavierisMoreno
mainlyFernández-Villamil
due to the economy of scale phenomenon: since the production capacity has been69
set low given the novelty and the risk of the project, the profitability is also low. A possible
solution would be to increase the production capacity by adding a reactor battery in series or
parallel to the already proposed solution, once the project has been carried out and proven to
work. On the other hand, it is important to notice that no benefit has been considered from
subsidies from the European Union, which are fairly common in this type of processes, as
discussed in the market review.
11.4 Sensitivity analysis.
Some of the values used in this economic analysis are estimations and are subject to changes in
the future stages of the project. In order to support the validity of these estimations, a sensitivity
analysis is presented. A sensitivity analysis is a useful tool to show the effect of varying a
specific parameter in the economic viability of the project. The chosen parameters are two:
product price and fixed capital investment. For each of them, the cumulative cash flow over the
plant´s life spam and the net present value for a discount rate of 10 % will be presented.
Ethanol prices have been very volatile in the past years, so estimating the effect of its variation in
the years to come is highly relevant. On the other hand, the fixed capital investment has been
calculated from equipment costs through basic formulas, and it is subject to changes in the next
stages of the project which can be studied through this analysis. Furthermore, the fixed capital
investment is also used to determine some of the terms in the fixed operation costs, which
amount to up to 59 % of the manufacturing costs. As for the variable operation costs, the biggest
contributor is electricity, but since the cost of electricity in Finland is fairly stable it will not be
included in the analysis.
Fixed capital investment.

Fixed capital investment has been varied between 4 and 6,7 million euros (±25 %). As seen in
Figure 18, the latter scenario is highly undesirable, as it would take 13 years to recover the initial
investment. Nevertheless, Figure 19 shows net present value is always positive, showing
profitability even in the worst case scenario. Varying the fixed capital investment also varies the
estimated fixed operation costs, which can be seen in the cumulative cash flow.
Figure 18. Cumulative cash flow over the years at varying fixed investment costs (± 25 %).

Figure 19. Net present value over the plant´s life spam for a discount rate of 10 %. At different fixed capital
investments. Left column represents present scenario.
Ethanol price.
Ethanol prices have varied greatly in the past years due to changes in legislation and a reduction
in gasoline consumption. Furthermore, the price for second generation biofuels is still unclear, as
discussed in the market review. As a result, the price of ethanol has been varied between 554 and
677 € per ton (±10 %) in order to determine the effect on the economic viability. As seen in
Figure 20, ethanol price has a high impact on the annual cash flow, even at a lower variation
range than the fixed capital investment.
Figure 20. Cumulative cash flow over the plant´s life spam at varying ethanol prices (± 10 %).

For the lower level of ethanol price, NPV is nearly zero. The effect that ethanol prices have on
the viability of the project deserves further study, as it greatly increases the uncertainty of the
economic analysis. Nonetheless, incentives offered from the EU as part of the Horizon 2020
program and the compromise of the Finnish government to comply with the Paris Agreement
ensure stability in the second generation biofuels market, so stable prices are expected in the
future.
Figure 21. Net present value over the plant´s life spam for a discount rate of 10 % at different ethanol prices. Left
column represents present scenario.
11.5 Ethanol production vs. electricity generation.
As discussed earlier, the design and execution of this project is based on the premise that the
previous use of Tornio´s steel mill flue gases (electricity generation) is less profitable than
ethanol production. As to this moment, this premise has not yet been proved. By using the
simulation results, it is possible to know how much gas is used in the process, and the amount of
ethanol obtained from that gas. These results are summarized in Table 34:
Table 34. Gas inlet and outlet composition and quantities.
INPUT OUTPUT CONSUMED

Molar flow (kmol/h) 429,06 389,32 36,74
CO 369 299,2 69,8
H2 17,2 5,4 11,8
CO2 21,5 63,2 -41,7
N2 21,5 21,5 0
Electricity is obtained from syngas through a thermodynamic cycle known as the Rankine cycle,
in which the gas is burned in a boiler in order to produce steam which is then used to generate
electricity through a turbine [62]. Out of all the components in the syngas, only carbon monoxide

and hydrogen can be burned. Reactions 15 and 16 show the reactions of combustion and the
standard heat of combustion for CO and H2, respectively:
1 0
= −283 𝑺𝑺/𝑺𝑺𝑺 (15)
𝑺𝑺 + 𝑺2 ⟶𝑺𝑺2
2
∆𝑺
𝑺
2 𝑺2 + 𝑺2 ⟶ 2 𝑺2 𝑺 ∆𝑺𝑺0 = −285,8 𝑺𝑺/𝑺𝑺𝑺 (16)
Figure 22. Rankine cycle.
Considering all of the CO and H2 that is consumed in the process would burned in the boiler, the
standard heat of combustion and the mole flow can be used to determine the heat supply to the
cycle:
𝑺 = ∆𝑺0 ∙𝑺 + ∆𝑺0 ∙𝑺 = 283 ∙ 69800 + 285,8 ∙ 11800 = 6423,8 𝑺𝑺 (17)

𝑺 𝑺𝑺 𝑺 𝑺 𝑺2 𝑺
𝑺 3600 3600
2
The efficiency of this process is determined by the parameters of the cycle used. Typical
efficiencies for the modified Rankine cycles used in this type of processes range from 32 % to
42 %, whereas operation costs range from 0,02 to 0,04 €/kWh [63,64]. As of this, the electric
power obtained from the syngas and the operation costs are:
𝑺 = 6423,8 ∙ 0,37 = 2376,8 𝑺𝑺 (18)
𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺 = 0,03 €/kWh ∙ 0,66 kWh/s = 0,0198 €/s = 570 240 €/year (19)
The cost of electricity in the Finnish industry is 50 €/MWh. The annual revenue that would thus
be obtained from the consumed gas is 950 720 € per year, which yields a yearly profit of 380 480
€. On the other hand, the annual profit obtained from using the same amount of gas for ethanol
production is, as shown in Table 31, 721 129 € per year. This is more almost twice the savings
obtained from electricity generation. Table 35 summarizes these results.
Table 35. Economic benefit of generating electricity vs. ethanol production.
Ethanol production Electricity generation

Annual profit Annual profit
Production (tons/year) Power (kW)
(€/year) (€/year)
4888 721 129 2376,8 380 480
As a result, the potential economic benefit from the transformation of syngas into ethanol
through fermentation is higher than the current use given to the gas in Tornio´s steel mill,
justifying the design and execution of the project.

12. SOCIAL, ETHICAL AND PROFESSIONAL RESPONSIBILITY.
12.1 Social issues.
Second generation biofuels are opening a cost-effective and efficient gateway to reduce
greenhouse gas emissions while avoiding any interference in the agricultural markets, unlike
biofuels made from corn and starch. Through the use of waste gases as feedstock to make fuel,
domestic economic growth is promoted in a sustainable way by avoiding competition with land,
food, and water resources.
The steel maker Outokumpu has put a big interest on this project, as the positive effect it has in
the environment is also translated in a improved social image, given the increasing concern on
climate change. Furthermore, Outokumpu is also deeply involved in the safety of the workers in
its plants. This is why precautions and security measures regarding chemicals involved in the
process have been described in “Safety”.
12.2 Ethical and legal considerations.
If Outokumpu decides to carry out the project, legal regulations and compliance of safety
measures must be ensured in order to build and run the plant, according to Finnish standards.
The petrochemical company Neste Oil has also shown interest in the design of this project, but as
the author of this work I would like to make clear my will not to have any type of involvement
with this company. In order to establish itself as one of the world´s main palm oil producers,
Neste Oil has been involved in illegal deforestation in Indonesia and Malaysia at the expense of
local inhabitants [65]. It is therefore my desire to forbid the use of any of this material by any
person involved in the company.
12.3 Environmental impact.
As discussed in chapter 9, the use of flue gases coming from the steel mill in Tornio to produce
ethanol reduces carbon emission by more than 1700 tons per year. The environmental impact of
the plant is further reduced by recirculating most of the water back to the bioreactor. This
situation could be further improved by studying the possibility of increasing production capacity
by adding more bioreactors, once the proposed solution is proved to work without any setbacks.

13. CONCLUSION AND FUTURE PROSPECTIVE.
The European Union has declared low carbon biofuels as the fastest and most cost-efficient
method to reduce greenhouse gas emissions in order to comply with the objectives of the Paris
Agreement. The incentives and subsidies offered as a result are changing the way companies
view waste, and second generation biofuels made from industrial flue gases are gaining
importance in the fuel market. This work is a result of this effort.
The objective of this project is to lay the basics for the design of a plant capable of transforming
the flue gases from Outokumpu´s steel mill in Tornio, Finland, into ethanol through gas
fermentation. The process, which consists of four basic operations (bacterial growth, gas
pretreatment, fermentation and product separation), has been simulated using Aspen Plus ®. The
conclusions extracted from the work done are the following:
 The biofuel market in Finland is ensured to prosper due to a national law that requires
fuel distributors to provide biofuels to the market. This situation leads to a growing
domestic ethanol market in the country, as seen from the increasing production of ethanol
by different Finnish companies.
 As mentioned, the process is divided into four operations: bacterial growth, gas
pretreatment, fermentation and product separation. The strain of bacteria chosen for the
process is Clostridium Ljungdahlii, due to the wide research available on it. Gas
pretreatment consists of pressure increase through compression and consequent
temperature decrease, all of which were properly studied using sensitivity analysis tools.
As for product separation, simple distillation is the selected method due to the maturity of
the technology.
 The bioreactor selected is airlift reactor OKTOP® 9000, an airlift reactor produced by a
well known Finnish company by the name of Outotec. The KLa value of the reactor
defines the mass transfer rate and it has a value of 18 h-1. Mass transfer is the bottleneck
of the process, and as such was modeled in the simulations.
 Reactor modeling in the simulation was made according to gas-liquid mass transfer rates,
whereas the amount of gas used in the process also proved to be relevant. This amount
was selected according to a sensitivity analysis on productivity: 429 kmol/h or 30 % of
the total amount of gas produced in the steel mill.

 In total, 4888 tons per year of ethanol 96 % pure in weight are produced every year. After
separation of bacteria, most of the water is recirculated back to the reactor to minimize
environmental impact.
 1737 tons per year of carbon are captured in the process. The use of the steel mill flue
gases to produce ethanol is thus more environmentally friendly than its current use, in
which carbon monoxide is flared to produce electricity and transformed into carbon
dioxide.
 A basic lay-out of the control of the process is also included as part of the standard design
of a chemical plant. The objective is to present a rough draft of the study and control of
the free variables that affect the bacterial growth, gas pretreatment, and fermentation
operations, excluding separation for simplicity reasons. The result of the study is the
P&ID diagram illustrating the instruments used to control and manipulate these variables.
 The use of steel mill flue gases to produce ethanol instead of electricity has also proven to
be more economically beneficial, yielding almost twice as much annual profit. As a result,
the economic interest in the venture is justified.
 According to the economic analysis, annual cash flow when the productivity of the plant
is 100 % is 720 000 €, which give a payback period of 10 years. This value is remarkably
high considering a life-span of the plant of 20 years. However, this scenario is a
pessimistic one given that no subsidies have been considered, yet as seen in other similar
projects there is substantial aid from the EU and the Finnish government.
 The sensitivity analysis presented to support the economic benefit of the venture shows
that ethanol prices have a considerable impact on the profitability of this project.
Nonetheless, incentives offered from the EU as part of the Horizon 2020 program and the
compromise of the Finnish government to comply with the Paris Agreement ensure
stability in the second generation biofuels market, so stability of the prices is expected in
the future.
 Through the use of waste gases as feedstock to make fuel, domestic economic growth is
promoted in a sustainable way by avoiding competition with land, food, and water
resources. As a result, the overall economic, environmental and social impacts of the
project are expected to be beneficial.
As mentioned earlier, the project is an outline showing the basic steps of chemical plant design.
The motivation behind it is mainly educational, and as such there are many points that deserve
further study and research.

One of them, and probably the most crucial for the success of the project, is the design of the
bioreactor. The selection of the reactor for this operation has been made according to the
recommendations of Professor Tuomas Koiranen, but it is important to point out that the
performance of the OKTOP® 9000 is still under research. Another option, the most conservative
one, would be to use a standard bubble column reactor. Either way, KLa values were used as a
reference parameter of selection since there was no possibility of undergoing real experiments.
Nonetheless, using a pilot model of the reactor and making proper investigations of its
applicability in this process is highly recommended.
Another parameter that escapes the reach of this project is the adaptation process of the bacteria
strain. Clostridium Ljungdahlii was the selected strain for the project given the wide information
available on it. However, this is only the beginning. Every chemical process that uses bacteria for
fermentation must undergo prior genetic modifications of the bacteria so it can perform correctly.
An important advantage of using genetic engineering in the bacteria is the possibility of

increasing product portfolio. Ethanol is only one of the many products that could be obtained,
but there are others that may very well increase profitability. One such example is acetic acid or
2,3 butanediol, the last of which is highly profitable. There are numerous studies that hint that
these products could be obtained in feasible amounts for separations through the correct genetic
engineering tools on C. Ljungdahlii [66, 67, 68]. Many important players in the industrial waste
fermentation industry are already focusing on this matter to further increase the profitability of
their plants. In order for this to take place, productivity shall also be increased, which takes us
another issue that should be further studied.
Following the principle of economy of scale, producing more means producing at a lower
operation cost per unit of product. In addition, increasing productivity means that valuable
byproducts could obtained in quantities big enough for separation to be feasible. Furthermore, it
was proved that using the steel mill flue gases for fermentation was more profitable than
electricity generation, so the bigger the production the better. Everything points out to the idea
that a bigger production is better. However, as mentioned earlier the project is too innovative and
there are many knots to tie, so for simplicity reasons productivity was kept low. The idea is that
once the plant is built and proved to work normally, more reactors could be added to the process
to increase productivity. The reactor configuration (parallel or series) and the possibility of
recirculating the gas would be the main points to address in order to carry out this project.

14. SCHEDULING AND BUDGET.
The project is a result of the course on Process and Plant design by Prof. Tuomas Koiranen. In
this course, the work was made in teams and consisted of four reports that simulated the different
stages the design of a chemical plant: literature review and market study, process design and
simulation, economic analysis and conclusions. The little knowledge of my team mates has
forced me to repeat the work so that it is presentable, resulting in an improved version of the
early project for which I take all authorship together with my team mate, Ali Saud.
The steps followed are the ones explained in Methodology. The hours invested in each step are
shown in Table 36, and the Gantt diagram can be seen in Figure 23. The writing of the report
was made along with every stage of the project, and modifications and corrections took place
from May to the 17th of July of 2017. As expected, the stage that took the longest time was the
simulation. I would like to mention the incredible effort that has been put behind this work, as I
myself had no previous experience with many of the subjects involved in the subject.
Table 36. Time distribution for each task.
TASK TIME (h)

MARKET REVIEW 30
LITERATURE REVIEW 80
PROCESS SELECTION 70
Specification of feedstock 20
Gas pretreatment 15
Bacterial growth 10
Fermentation 20
Product separation 5
PRODUCTION CAPACITY 20
SIMULATION AND OPTIMIZATION 180
PROCESS CONTROL 30
ECONOMIC ANALYSIS 60
Cost estimations 30
Sensitivity analysis 20
Ethanol production vs. electricity generation 10
WRITING OF REPORT 40
TOTAL 510
The total workload amounts to 510 hours.

14.1 Gantt chart.
Figure 23. Gantt chart.

14.2 Project budget.
The computer used for this project belongs to LUT University, as well as the licenses of the
different software used. Therefore, the project budget is calculated according to the work hours
spent in each stage. The student work is valued in 10 €/hour. The total budget is shown in the
following table:
Table 37. Project budget
Task Time (h) Cost (€/h) Total (€)

Market review 30 10 300
Literature review 80 10 800
Process selection 70 10 700
Production capacity 20 10 200
Simulation and
180 10 1800
optimization
Process control 30 10 300
Economic analysis 60 10 600
Writing of report 40 10 400
TOTAL 510 10 5100
In total, the cost of this project is 5100 €.

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Process and plant design of ethanol synthesis from steel industry flue gas

Javier Moreno Fernández-Villamil

Javier Moreno Fernández-

DIRECTORA DEL TRABAJO DE FIN DE GRADO:

Lima, 15th of July of 2017.

Javier Moreno Fernández-Villamil 1

2 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Javier Moreno Fernández-Villamil 3

LIST OF TABLES .......................................................................................................................... 6

4 Escuela Técnica Superior de Ingenieros Industriales (UPM)

10. SAFETY ................................................................................................................................. 57

Javier Moreno Fernández-Villamil 5

Table 1. Review of main companies currently working on gas fermentation. ............................. 11

6 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Javier Moreno Fernández-Villamil 7

PSL Partial pressure of the substrate in the liquid phase

8 Escuela Técnica Superior de Ingenieros Industriales (UPM)

MEE Ministry of Employment and Economy

Javier Moreno Fernández-Villamil 9

10 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Table 1. Review of main companies currently working on gas fermentation.

Javier Moreno Fernández-Villamil 11

12 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Javier Moreno Fernández-Villamil 13

14 Escuela Técnica Superior de Ingenieros Industriales (UPM)

4.1 Biofuel or fossil fuel?

Javier Moreno Fernández-Villamil 15

4.2 Supply and demand

16 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Javier Moreno Fernández-Villamil 17

18 Escuela Técnica Superior de Ingenieros Industriales (UPM)

5. PROCESS OVERVIEW AND DESIGN

Javier Moreno Fernández-Villamil 19

Javier Moreno Fernández-Villamil 21

5.2 Gas cleaning and pretreatment

other hand, temperature is settled by bacteria specifications, which will be discussed in

5.3 Bacterial growth

Table 3. Main species of bacteria capable of syngas fermentation [31].

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5.4 Gas fermentation

Javier Moreno Fernández-Villamil 23

5.4.1 Reaction stoichiometry and kinetics

6 𝑺𝑺 + 3 𝑺2𝑺 ⟶𝑺2𝑺5𝑺𝑺 + 4 𝑺𝑺2 ∆𝑺 = −217,9 𝑺𝑺/𝑺𝑺𝑺 (2)

2 𝑺𝑺2 + 4 𝑺2 ⟶𝑺𝑺3𝑺𝑺𝑺𝑺 + 2 𝑺2𝑺 ∆𝑺 = −75,3 𝑺𝑺/𝑺𝑺𝑺 (5)

As mentioned, the rate-limiting step in reactions 2 to 5 is the dissolution of the gaseous

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5.4.2 Reactor specifications

Javier Moreno Fernández-Villamil 25

Table 4. Performance parameters of various bioreactor configurations [42].

Figure 5. Different configurations of bubble-driven bioreactors [42].

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Table 5. Performance parameters of the OKTOP® 9000 airlift reactor.

Gas Holdup 20-30%

6 𝑺𝑺 + 3 𝑺 𝑺 ⟶𝑺 𝑺 𝑺𝑺 + 4 𝑺𝑺 𝑺 = 4,01 ∙ 10−8 ( ) (8)

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Figure 6. Reactor specifications.

Javier Moreno Fernández-Villamil 29

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Javier Moreno Fernández-Villamil 31

𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 𝑺𝑺𝑺𝑺𝑺𝑺 𝑺ℎ𝑺

5.5 Product recovery and separation of bacteria

Thermodynamic properties at 1 bar regarding the separation of a mixture containing water,

As specified earlier, further purification of ethanol is neglected for simplicity reasons. An